Methods for reducing the population of arthropods with medium chain peroxycarboxylic acid compositions

ABSTRACT

The present invention relates to methods for reducing the population of (e.g., killing) arthropods employing compositions including medium chain peroxycarboxylic acid, and to the compositions. The methods include applying a medium chain peroxycarboxylic acid composition to an arthropod or a surface or area suspected of housing an arthropod.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims priority as a continuation in part toU.S. patent application Ser. No. 11/030,641, filed Jan. 4, 2005, andSer. No. 10/754,426, filed Jan. 9, 2004, the disclosures of which areincorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to methods for reducing the population of(e.g., killing) arthropods employing compositions including medium chainperoxycarboxylic acid, and to the compositions. The methods includeapplying a medium chain peroxycarboxylic acid composition to anarthropod or a surface or area suspected of housing an arthropod.

BACKGROUND OF THE INVENTION

Conventional peroxycarboxylic acid compositions typically include shortchain peroxycarboxylic acids or mixtures of short chain peroxycarboxylicacids and medium chain peroxycarboxylic acids (see, e.g., U.S. Pat. Nos.5,200,189, 5,314,687, 5,409,713, 5,437,868, 5,489,434, 6,674,538,6,010,729, 6,111,963, and 6,514,556). Medium chain peroxycarboxylic acidcompositions have been developed for antimicrobial applications, buthave not previously been observed to have activity against arthropods.

Arthropod (e.g., insect) pests have plagued mankind for millennia.Consumers and businesses spend billions of dollars each year on goodsand services aimed at controlling these pests. Unfortunately, many pestcontrol agents are toxic to humans or smell bad.

There remains a need for compositions that can reduce an arthropodpopulation, for example, without unacceptable toxicity to humans.

SUMMARY OF THE INVENTION

The present invention relates to methods for reducing the population of(e.g., killing) arthropods employing compositions including medium chainperoxycarboxylic acid, and to the compositions. The methods includeapplying a medium chain peroxycarboxylic acid composition to anarthropod or a surface or area suspected of housing an arthropod.

The compositions of the invention and other medium chainperoxycarboxylic acid antimicrobial compositions can be employed inmethods for reducing the population of (e.g., killing) an arthropod.These methods include applying to the arthropod or to a surface orregion suspected of housing an arthropod a medium chain peroxycarboxylicacid antimicrobial composition, for example in an amount and timesufficient to reduce the population of the arthropod or to kill thearthropod. The composition can be applied by methods including sprayingand foaming. In an embodiment, the method includes contacting thearthropod with a foamed composition.

In an embodiment, the method of the present invention can kill or reducethe population of any of a variety of arthropods, such as an insect, anarachnid, a centipede, or the like. In an embodiment, the method cankill or reduce the population of any of a variety of forms of thearthropod. For example, the method can be effective against an arthropodegg. In an embodiment, the present method kills a cockroach egg. By wayof further example, the method can be effective against an arthropodlarvae.

In an embodiment, the antimicrobial composition of the present inventionincludes medium chain peroxycarboxylic acid, solubilizer, oxidizingagent, and acidulant. Such a composition can include about 0.0005 toabout 5 wt-% medium chain peroxycarboxylic acid; about 0.001 to about 10wt-% medium chain carboxylic acid; about 0 to about 99.99 wt-% water;and about 0.001 to about 80 wt-% solubilizer effective for solubilizingthe medium chain peroxycarboxylic acid and the medium chain carboxylicacid. The composition can include a microemulsion and/or about 2 or moreparts by weight of medium chain peroxycarboxylic acid for each 7 partsby weight of medium chain carboxylic acid. In use form, the medium chainperoxycarboxylic acid composition can include about 2 to about 500 ppmmedium chain peroxycarboxylic acid, about 5 to about 2000 ppm mediumchain carboxylic acid, about 95 to about 99.99 wt-% water; and about 2to about 16,000 ppm solubilizer.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

As used herein, the phrase “medium chain carboxylic acid” refers to acarboxylic acid that: 1) has reduced or is lacking odor compared to thebad, pungent, or acrid odor associated with an equal concentration ofsmall chain carboxylic acid, and 2) has a critical micellarconcentration greater than 1 mM in aqueous buffers at neutral pH. Mediumchain carboxylic acids exclude carboxylic acids that are infinitelysoluble in or miscible with water at 20° C. Medium chain carboxylicacids include carboxylic acids with boiling points (at 760 mm Hgpressure) of 180 to 300° C. In an embodiment, medium chain carboxylicacids include carboxylic acids with boiling points (at 760 mm Hgpressure) of 200 to 300° C. In an embodiment, medium chain carboxylicacids include those with solubility in water of less than 1 g/L at 25°C. Examples of medium chain carboxylic acids include pentanoic acid,hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoicacid, undecanoic acid, and dodecanoic acid.

As used herein, the phrase “medium chain peroxycarboxylic acid” refersto the peroxycarboxylic acid form of a medium chain carboxylic acid.

As used herein, the phrase “short chain carboxylic acid” refers to acarboxylic acid that: 1) has characteristic bad, pungent, or acrid odor,and 2) is infinitely soluble in or miscible with water at 20° C.Examples of short chain carboxylic acids include formic acid, aceticacid, propionic acid, and butyric acid.

As used herein, the phrase “short chain peroxycarboxylic acid” refers tothe peroxycarboxylic acid form of a short chain carboxylic acid.

As used herein, the term “solubilizer” refers to a component of thepresent compositions to that makes soluble or increases the solubilityin a carrier (e.g., water) of the medium chain carboxylic acid, mediumchain peroxycarboxylic acid, or mixture thereof. For example, in anembodiment, the solubilizer can keep a composition including mediumchain carboxylic acid, medium chain peroxycarboxylic acid, or mixturethereof in solution or can keep the composition finely and evenlydispersed under ordinary storage conditions without forming a separatelayer. The solubilizer can, for example, solubilize a medium chaincarboxylic acid to an extent sufficient to allow it to react with anoxidizing agent, such as hydrogen peroxide. A solubilizer can beidentified by a test that measures phase separation under ordinarystorage conditions, such as room temperature, 100° F., or 60° C. As usedherein, the term “solubilizer” does not include short chain carboxylicacids; they are not solubilizers.

As used herein, the term “microemulsion” refers to a thermodynamicallystable dispersion of one liquid phase into another stabilized by aninterfacial film of surfactant. The dispersion can be oil-in-water orwater-in-oil. Microemulsions are typically clear solutions when thedroplet diameter is approximately 100 nanometers or less. In anembodiment, the present microemulsion composition is a shear thinningviscoelastic gel that has a blue tyndall appearance.

As used herein, the phrases “blue tyndall appearance” or “blue tyndall”refer to a bluish hue due to scattering of blue light or the blue regionof the light spectrum.

As used herein, the phrases “viscoelastic gel” and “viscoelastic liquid”refer to a liquid composition that exhibits both viscous and elasticcharacteristics or responses, which is indicative of long range order orstructure.

As used herein, a composition or combination “consisting essentially” ofcertain ingredients refers to a composition including those ingredientsand lacking any ingredient that materially affects the basic and novelcharacteristics of the composition or method. The phrase “consistingessentially of” excludes from the claimed compositions and methods shortchain carboxylic acids, short chain peroxycarboxylic acids, or mixturesthereof; unless such an ingredient is specifically listed after thephrase.

As used herein, a composition or combination “substantially free of” oneor more ingredients refers to a composition that includes none of thatingredient or that includes only trace or incidental amounts of thatingredient. Trace or incidental amounts can include the amount of theingredient found in another ingredient as an impurity or that isgenerated in a minor side reaction during formation or degradation ofthe medium chain peroxycarboxylic acid.

As used herein, the phrase “a level insufficient to solubilize” refersto a concentration of an ingredient at which the ingredient is notsufficient to solubilize an insoluble material and to keep thecomposition substantially in one phase.

As used herein, the phrases “objectionable odor”, “offensive odor”, or“malodor” refer to a sharp, pungent, or acrid odor or atmosphericenvironment from which a typical person withdraws if they are able to.Hedonic tone provides a measure of the degree to which an odor ispleasant or unpleasant. An “objectionable odor”, “offensive odor”, or“malodor” has an hedonic tone rating it as unpleasant as or moreunpleasant than a solution of 5 wt-% acetic acid, propionic acid,butyric acid, or mixtures thereof.

As used herein, the term “arthropod” refers to any of a phylum ofinvertebrate animals that have a segmented body and jointed appendages.Arthropods can have a chitinous exoskeleton that is molted at intervalsand/or a dorsal anterior brain connected to a ventral chain of ganglia.Arthropods have a chitinous segmented exoskeleton that encloses abilaterally symmetric body cavity and paired appendages. As used herein,insects, arachnids, chilopods (e.g., centipedes) diplopods (e.g.,millipedes), scorpions, and crustaceans are considered arthropods.Arthropods of interest with respect to the present invention includethose of public health significance, such as blood feeders (ticks, bedbugs, biting flies, mosquitoes, etc.), biting/stinging arthropods(“poisonous” spiders, bees, wasps, ants, etc.), and potentialtransmitters of disease (filth flies, cockroaches, dust mites, lice,etc.). Other arthropods of interest relating to the present inventioninclude most arthropods considered pests that can cause significanteconomic damage. Pest arthropods of interest include small (drain)flies, fruit flies, fabric pests (moths and beetles), plant leaf pests(aphids, whiteflies, scales, leaf miners, mites, caterpillars, etc.),occasional invaders (boxelder bugs, ladybugs, ground beetles, sowbugs,etc.), stored product pests (flour beetles, weevils, grain borers, etc.)and wood destroying insects (termites, powder post beetles, barkbeetles, wood boring beetles, etc.).

As used herein, the term “insect” refers to a general category of smallinvertebrate animals of the class Insecta that are more or lessobviously segmented. Bugs, bees, spiders, and centipedes are insects.

As used herein, the term “Insecta” refers to arthropods that have awell-defined head, thorax, abdomen, and only three pairs of legs.Insecta can have, for example, one or two pairs of wings. Bugs and beesare Insecta.

As used herein, the terms “mixed” or “mixture” when used relating to“peroxycarboxylic acid composition” or “peroxycarboxylic acids” refer toa composition or mixture including more than one peroxycarboxylic acid,such as a composition or mixture including peroxyacetic acid andperoxyoctanoic acid.

As used herein, the phrase “densified fluid” refers to a fluid in acritical, subcritical, near critical, or supercritical state. The fluidis generally a gas at standard conditions of one atmosphere pressure and0° C. As used herein, the phrase “supercritical fluid” refers to a densegas that is maintained above its critical temperature, the temperatureabove which it cannot be liquefied by pressure. Supercritical fluids aretypically less viscous and diffuse more readily than liquids. In anembodiment, a densified fluid is at, above, or slightly below itscritical point. As used herein, the phrase “critical point” is thetransition point at which the liquid and gaseous states of a substancemerge into each other and represents the combination of the criticaltemperature and critical pressure for a substance. The critical pressureis a pressure just sufficient to cause the appearance of two phases atthe critical temperature. Critical temperatures and pressures have beenreported for numerous organic and inorganic compounds and severalelements.

As used herein, the terms “near critical” fluid or “subcritical” fluidrefer to a fluid material that is typically below the criticaltemperature of a supercritical fluid, but remains in a fluid state anddenser than a typical gas due to the effects of pressure on the fluid.In an embodiment, a subcritical or near critical fluid is at atemperature and/or pressure just below its critical point. For example,a subcritical or near critical fluid can be below its criticaltemperature but above its critical pressure, below its critical pressurebut above its critical temperature, or below both its criticaltemperature and pressure. The terms near critical and subcritical do notrefer to materials in their ordinary gaseous or liquid state.

As used herein, the term “about” modifying the quantity of an ingredientin the compositions of the invention or employed in the methods of theinvention refers to variation in the numerical quantity that can occur,for example, through typical measuring and liquid handling proceduresused for making concentrates or use solutions in the real world; throughinadvertent error in these procedures; through differences in themanufacture, source, or purity of the ingredients employed to make thecompositions or carry out the methods; and the like. The term about alsoencompasses amounts that differ due to different equilibrium conditionsfor a composition resulting from a particular initial mixture. Whetheror not modified by the term “about”, the claims include equivalents tothe quantities.

Methods of Reducing Arthropod Population

The present invention relates to methods for reducing the population of(e.g., killing) an arthropod employing compositions including mediumchain peroxycarboxylic acid, and to the compositions. The methodsinclude applying a medium chain peroxycarboxylic acid composition to anarthropod or a surface or area suspected of housing an arthropod. Themethod can include contacting the arthropod with the medium chainperoxycarboxylic acid composition in an amount and time sufficient tokill the arthropod. As used herein, the term killing includes renderingmoribund and rendering lifeless.

The composition can be applied by any of a variety of methods suitablefor applying an agent such as an insecticide. For example, the methodcan include applying the composition by spraying (e.g., aerosolspraying) or foaming. Other suitable methods for applying thecomposition include drenching or soaking.

The spray can be applied as a wet spray or an aerosol spray. As usedherein, the phrase “wet spray” refers to water or solvent based liquidcontaining the composition where pressure is used to expel spray onto orinto desired areas. A wet spray can include stream or large dropletspray patterns. In contrast, in an aerosol spray, a water or solventbased liquid containing the composition where air is both used to expelthe liquid and is mixed with the liquid resulting in smaller particlesizes. Aerosol sprays can be applied by methods or equipment includingin an aerosol can and with aerosol generating equipment such as theActisol® machine. Wet sprays can be applied using equipment such astrigger sprayers and compressed air sprayers.

The present method can include contacting any of a variety of arthropodsor forms of an arthropod. For example, the method can include killing orreducing the population of eggs or larvae. In particular, cockroach eggshave been difficult to kill with conventional insecticides.Advantageously, the present medium chain peroxycarboxylic acidcomposition has proven effective in killing cockroach eggs. Additionalarthropod eggs that can be killed according to the present inventioninclude house fly eggs and fruit fly eggs. The present method andcomposition can also be useful in killing eggs of plant feeding insectson food crops and ornamental plants as well as eggs of insects such as,for example, mosquitoes, lice, fleas, spiders, and booklice.

The present method employing the medium chain peroxycarboxylic acidcomposition has proven effective in killing larvae of arthropods. Forexample, the present methods and compositions have effectively killedfruit fly larvae. Additional arthropod larvae that can be killedaccording to the present invention include beetle larvae and other flylarvae. Many insects such as lepidopteran larvae do much of theireconomic damage as larvae where the present method and composition canbe effective.

The present method can include applying the medium chainperoxycarboxylic acid compositions in any of a variety of locations orsituations. In particular, the present foaming compositions can beadvantageously applied to cavities, such as those in walls or under,behind, or in equipment or appliances. Additional locations andsituations for applying the present compositions include wherever liveinsects are seen or thought to harbor.

In an embodiment, the present method includes applying a compositionincluding a high concentration of medium chain peroxyoctanoic acid andcontacting the arthropod with a low volume of the composition perarthropod. In an embodiment, the present method includes applying acomposition including a low concentration of medium chain peroxyoctanoicacid and contacting the arthropod with a high volume of the compositionper arthropod.

The present method can include applying the medium chainperoxycarboxylic acid composition in any of a variety of situations toreduce the population of any of a variety of arthropods, such asinsects. For example, the present method can include applying thecomposition in a food processing or preparation situations. The presentmethod can include applying the medium chain peroxycarboxylic acidcomposition to a food product (e.g., a fruit or a vegetable) to kill aninsect on the food product. The present method can include applying themedium chain peroxycarboxylic acid composition through automatedspraying or foam dispensing under a cook line. The present method caninclude applying the medium chain peroxycarboxylic acid composition to adrain, drain line, or sewer. Foaming compositions can fill the drain ordrain line.

Advantageously, a foaming preparation of the present composition can beapplied in a void and, in an embodiment, be employed to fill the void.In an embodiment, filling the void can include contacting all surfacesand pest life stages within. Suitable voids include those inside a baror booth, inside equipment, inside a wall, under a slab, inside a tube,inside hollow furniture, behind shelving or store fixtures, or insidedrawer, drain line, or piping. Advantageously, a foaming preparation ofthe present composition remain or stick on a surface, e.g., a verticalsurface or the bottom of a horizontal surface.

By way of further example, the present method can include applying themedium chain peroxycarboxylic acid composition in outdoor oragricultural situations. The present method can include applying thecompositions to plants (e.g., crop, tree, or shrub) through spraying,such as aerial spraying or power spraying (e.g., employing a boomsprayer). The present method can include applying the composition tomulch or as a foam barrier around a structure or piece of equipment. Thepresent method can include applying the composition on or into an insectnest. The present compositions can be applied to manure.

The present method can include applying the medium chainperoxycarboxylic acid composition at an acidic pH and then neutralizingafter applying. Such neutralization can reduce corrosion and/or aidcleaning.

Advantageously, at an acidic pH, the present compositions also reducethe population of one or more microbes. Accordingly, the present methodcan include applying the medium chain peroxycarboxylic acid compositionand reducing the population of an insect and reducing the population ofa microbe. The method can include simultaneously reducing the populationof an insect and reducing the population of a microbe. The method caninclude reducing the population of a microbe on a surface, in a region,or in a void which can then reduce the population of arthropod thatmoves into the area (the future arthropod population of the surface,region, or void). Fewer microbes on a surface, in a region, or in a voidcan make the surface, region, or void less habitable by or attractive toan arthropod.

In an embodiment, the present compositions can be employed incombination with other pest control methods or agents, such as a lighttrap, an attractant, a repellant, a pheromone, a growth regulator, or aresidual pesticide. The present composition can be applied eitherseparately from or mixed with another chemical. For example, applying anattractant with the present composition can attract an arthropod to becontacted and killed by the medium chain peroxycarboxylic acidcomposition. For example, applying a repellant with the presentcomposition can repel or deter an arthropod from one area to increasethe likelihood that it enters a treated area in which it can becontacted and killed by the medium chain peroxycarboxylic acidcomposition. For example, providing the present composition in a lighttrap can kill an arthropod attracted into the light trap by the light.For example, applying a pheromone with the present composition canattract or immobilize an arthropod to be contacted and killed by themedium chain peroxycarboxylic acid composition. For example, applying agrowth regulator with the present composition can maintain an arthropodin a particular growth state or advance an arthropod to a growth stateto be contacted and killed by the medium chain peroxycarboxylic acidcomposition. For example, applying a residual pesticide with the presentcomposition can provide longer term killing of an arthropod. Forexample, applying a residual pesticide with or near the presentcomposition can cause an arthropod to enter the present composition dueto temporarily increased activity (e.g., running around).Advantageously, such a method can decrease spread of allergens.

The present method can include applying the medium chainperoxycarboxylic acid composition and can include or omit rinsing. In anembodiment, the present method includes applying a low concentration ofmedium chain peroxycarboxylic acid composition (e.g., less than about 1wt-% or less than about 0.5 wt-%) and the method omits rinsing.

Foam Treating Arthropods

In another alternative embodiment of the present invention, thearthropod or surface or region suspected of housing an arthropod can betreated with a foaming version of the composition. The foam can beprepared by mixing foaming surfactants with the insecticidal solution attime of use. The foaming surfactants can be nonionic, anionic orcationic in nature. Examples of useful surfactant types include, but arenot limited to the following: alcohol ethoxylates, alcohol ethoxylatecarboxylate, amine oxides, alkyl sulfates, alkyl ether sulfate,sulfonates, quaternary ammonium compounds, alkyl sarcosines, betainesand alkyl amides. The foaming surfactant can be mixed at time of usewith the washing solution. Use solution levels of the foaming agents isfrom about 50 ppm to about 2.0 wt-%. At time of use, compressed air canbe injected into the mixture, then applied to the arthropod, surface, orregion through a foam application device such as a tank foamer or anaspirated wall mounted roamer.

Embodiments of the Present Method

In an embodiment, the present method includes a method of killing anarthropod. This embodiment of the method can include contacting anarthropod with a medium chain peroxycarboxylic acid composition in anamount and time sufficient to kill the arthropod. In this embodiment,the medium chain peroxycarboxylic acid composition can includeperoxyoctanoic acid. Such a composition can also include stabilizingagent.

In an embodiment, the method can include contacting the arthropod with acomposition including about 0.1 to about 20 wt-% of medium chainperoxycarboxylic acid composition. In an embodiment, the method caninclude contacting the arthropod with a foamed composition. In anembodiment, the method can include contacting the arthropod with a wetspray. In an embodiment, the method can include contacting the arthropodwith an aerosol spray.

In an embodiment, the method employs a composition including a highconcentration of medium chain peroxyoctanoic acid and the arthropod iscontacted with a low volume of the composition per arthropod. In anembodiment, the method employs a composition including a lowconcentration of medium chain peroxyoctanoic acid and the arthropod iscontacted with a high volume of the composition per arthropod.

In an embodiment, the arthropod includes or is an insect. In anembodiment, the arthropod includes or is an arachnid. In an embodiment,the arthropod includes or is an a centipede, millipede, or sow bug. Inan embodiment, the arthropod includes or is an arthropod egg. In anembodiment, the arthropod includes or is an arthropod larvae. In anembodiment, the present method includes a method of killing an arthropodegg. This embodiment of the method can include contacting an arthropodegg with a medium chain peroxycarboxylic acid composition in an amountand time sufficient to kill the arthropod egg. In this embodiment, themedium chain peroxycarboxylic acid composition can includeperoxyoctanoic acid. Such a composition can also include stabilizingagent.

In an embodiment, the method can include contacting the arthropod eggwith a composition including about 0.1 to about 20 wt-% of medium chainperoxycarboxylic acid composition. In an embodiment, the method caninclude contacting the arthropod egg with a foamed composition. In anembodiment, the method can include contacting the arthropod egg with awet spray. In an embodiment, the method can include contacting thearthropod egg with an aerosol spray.

In an embodiment, the arthropod egg is or includes a cockroach egg. Inan embodiment, the arthropod egg is or includes an insect egg. In anembodiment, the arthropod egg is or includes an arachnid egg. In anembodiment, the arthropod egg is or includes a centipede egg.

In an embodiment, the present method includes a method of killing anarthropod larva. This embodiment of the method can include contacting anarthropod larva with a medium chain peroxycarboxylic acid composition inan amount and time sufficient to kill the arthropod larva. In thisembodiment, the medium chain peroxycarboxylic acid composition caninclude peroxyoctanoic acid. Such a composition can also includestabilizing agent. In an embodiment, the arthropod larva is or includesan insect larva.

In an embodiment, the method can include contacting the arthropod larvawith a composition including about 0.1 to about 20 wt-% of medium chainperoxycarboxylic acid composition. In an embodiment, the method caninclude contacting the arthropod larva with a foamed composition. In anembodiment, the method can include contacting the arthropod larva with awet spray. In an embodiment, the method can include contacting thearthropod larva with an aerosol spray.

Suitable medium chain peroxycarboxylic acid compositions for use inthese embodiments of the invention can include about 0.0005 to about 5wt-% medium chain peroxycarboxylic acid; about 0.001 to about 10 wt-%medium chain carboxylic acid; about 0 to about 99.99 wt-% water; andabout 0.001 to about 80 wt-% solubilizer effective for solubilizing themedium chain peroxycarboxylic acid and the medium chain carboxylic acid.Such a composition can include about 2 or more parts by weight of mediumchain peroxycarboxylic acid for each 7 parts by weight of medium chaincarboxylic acid.

Suitable medium chain peroxycarboxylic acid compositions for use inthese embodiments of the invention can include about 0.5 to about 5 wt-%peroxyoctanoic acid; about 1 to about 10 wt-% octanoic acid; about 5 toabout 97 wt-% water; about 1 to about 20 wt-% anionic surfactant; about5 to about 10 wt-% oxidizing agent; about 15 to about 35 wt-% inorganicacid; and about 1 to about 5 wt-% sequestrant. Such a composition caninclude or can be in the form of a microemulsion.

Suitable medium chain peroxycarboxylic acid compositions for use inthese embodiments of the invention can include about 0.0005 to about 5wt-% peroxyoctanoic acid; about 0.001 to about 10 wt-% octanoic acid;about 40 to about 99.99 wt-% water; about 0.001 to about 60 wt-% atleast one of polyalkylene oxide, monoalkyl ether of polyalkylene oxide,dialkyl ether of polyalkylene oxide, anionic surfactant, and nonionicsurfactant; about 0.002 to about 10 wt-% oxidizing agent; about 0.001 toabout 30 wt-% inorganic acid; and about 0.001 to about 5 wt-%sequestrant.

Medium Chain Peroxycarboxylic Acid Antimicrobial Compositions

The present invention includes medium chain peroxycarboxylic acidcompositions. The present medium chain peroxycarboxylic acidcompositions can include increased levels of medium chainperoxycarboxylic acid compared to conventional peroxycarboxylic acidcompositions. The inventive compositions can include medium chainperoxycarboxylic acid and a solubilizer. The solubilizer can increase ormaintain the solubility of the medium chain peroxycarboxylic acid. Thepresent medium chain peroxycarboxylic acid compositions can include amicroemulsion or a surfactant that can form a microemulsion. The presentmedium chain peroxycarboxylic acid compositions need not includesubstantial amounts of short chain carboxylic acid, short chainperoxycarboxylic acid, or mixture thereof. It is believed that, inconventional mixed peroxycarboxylic acid compositions, the short chaincarboxylic acid, short chain peroxycarboxylic acid, or mixture thereofcan solubilize medium chain peroxycarboxylic acid.

In an embodiment, the present compositions include medium chainperoxycarboxylic acid. These compositions can also include medium chaincarboxylic acid. Such compositions can include advantageously highlevels of medium chain peroxycarboxylic acid. In an embodiment, thepresent compositions include about 2 or more parts by weight of mediumchain peroxycarboxylic acid for each 7 parts by weight of medium chaincarboxylic acid. In an embodiment, the present compositions includeabout 2 or more parts by weight of medium chain peroxycarboxylic acidfor each 6 parts by weight of medium chain carboxylic acid. In anembodiment, the present compositions include about 2 or more parts byweight of medium chain peroxycarboxylic acid for each 5 parts by weightof medium chain carboxylic acid. In an embodiment, the presentcompositions include about 2 or more parts by weight of medium chainperoxycarboxylic acid for each 4 parts by weight of medium chaincarboxylic acid. In an embodiment, the present compositions includeabout 2 parts by weight of medium chain peroxycarboxylic acid for each 3parts by weight of medium chain carboxylic acid.

In an embodiment, the present compositions include medium chainperoxycarboxylic acid and solubilizer. The solubilizer can include asolvent, a surfactant, or a mixture thereof. Suitable solvents includeany of a variety of solvents that solubilize and do not significantlydegrade the medium chain peroxycarboxylic acid. In certain embodiments,suitable solvents include polyalkylene oxide, capped polyalkylene oxide,mixtures thereof, or the like. Suitable solvents include nonionicsurfactant, such as alkoxylated surfactant. Suitable alkoxylatedsurfactants include, for example, EO/PO copolymer, capped EO/POcopolymer, alcohol alkoxylate, capped alcohol alkoxylate, mixturesthereof, or the like. When employed as a solvent a surfactant, such as anonionic surfactant, can be at concentrations higher than thoseconventionally employed.

The solubilizer can include surfactant (e.g., microemulsion formingsurfactant). Suitable surfactants include anionic surfactant, nonionicsurfactant, cationic surfactant, amphoteric surfactant, zwitterionicsurfactant, mixtures thereof, or the like. The solubilizer can include amicroemulsion forming surfactant. Suitable microemulsion formingsurfactants include anionic surfactant, cationic surfactant, amphotericsurfactant, zwitterionic surfactant, mixtures thereof, or the like.Suitable microemulsion forming surfactants include anionic surfactants,such as sulfate surfactant, sulfonate surfactant, phosphate surfactant(phosphate ester surfactant), and carboxylate surfactant, mixturesthereof, or the like.

In an embodiment, the present composition need not include substantialamounts of short chain peroxycarboxylic acid. For example, the presentcompositions can be free of added short chain peroxycarboxylic acid. Asused herein, free of added material refers to a composition thatincludes the material only as a incidental or trace quantity found, forexample, as an ingredient of or impurity in another named ingredient orincidentally generated from a minor side reaction.

In an embodiment, the present composition includes only relatively smallamounts of short chain peroxycarboxylic acid. For example, the presentcomposition can include about 1 or more parts of medium chainperoxycarboxylic acid for each 8 parts of short chain carboxylic acid,short chain peroxycarboxylic acid, or mixture thereof. For example, thepresent composition can include short chain peroxycarboxylic acid at alevel insufficient to cause odor offensive to a typical person.

In certain embodiments, the present composition does not includesubstantial amounts of peroxyacetic acid, is free of added peroxyaceticacid, includes about 1 or more parts of medium chain peroxycarboxylicacid for each 8 parts of peroxyacetic acid, or includes peroxyaceticacid at a level insufficient to cause odor offensive to a typicalperson.

In an embodiment, the present composition need not include substantialamounts of short chain carboxylic acid. For example, the presentcompositions can be free of added short chain carboxylic acid. In anembodiment, the present composition includes only relatively smallamounts of short chain carboxylic acid. By way of further example, thepresent composition can include about 1 or more parts of medium chainperoxycarboxylic acid for each 8 parts of short chain carboxylic acid.For example, the present composition can include short chain carboxylicacid at a level insufficient to cause odor offensive to a typicalperson.

In certain embodiments, the present composition does not includesubstantial amounts of acetic acid, is free of added acetic acid,includes about 1 or more parts of medium chain peroxycarboxylic acid foreach 8 parts of acetic acid, or includes acetic acid at a levelinsufficient to cause odor offensive to a typical person. In certainembodiments, the present compositions include, for example, less than 10wt-%, less than less than 5 wt-%, less than 2 wt-%, or less than 1 wt-%acetic acid. In certain embodiments, the present use compositionsinclude, for example, less than 40 ppm, less than 20 ppm, less than 10ppm, or less than 5 ppm acetic acid.

In an embodiment, the present composition need not include substantialamounts of short chain peroxycarboxylic acid, short chain carboxylicacid, or mixture thereof. For example, the present compositions can befree of added short chain peroxycarboxylic acid, short chain carboxylicacid, or mixture thereof. For example, the present composition caninclude short chain carboxylic acid, short chain peroxycarboxylic acid,or mixture thereof at a level insufficient to cause odor offensive to atypical person. In certain embodiments, the present composition does notinclude substantial amounts of acetic acid, peroxyacetic acid, ormixtures thereof; is free of added acetic acid, peroxyacetic acid, ormixtures thereof; includes about 1 or more parts of medium chainperoxycarboxylic acid for each 8 parts of acetic acid, peroxyaceticacid, or mixtures thereof; or includes acetic acid, peroxyacetic acid,or mixtures thereof at a level insufficient to cause odor offensive to atypical person.

In an embodiment, the present composition includes about 1 or more partsof medium chain peroxycarboxylic acid for each 8 parts of short chaincarboxylic acid, short chain peroxycarboxylic acid, or mixture thereof.In an embodiment, the present composition includes about 1 or more partsof medium chain peroxycarboxylic acid for each 7 parts of short chaincarboxylic acid, short chain peroxycarboxylic acid, or mixture thereof.In an embodiment, the present composition includes about 1 or more partsof medium chain peroxycarboxylic acid for each 6 parts of short chaincarboxylic acid, short chain peroxycarboxylic acid, or mixture thereof.In an embodiment, the present composition includes about 1 or more partsof medium chain peroxycarboxylic acid for each 5 parts of short chaincarboxylic acid, short chain peroxycarboxylic acid, or mixture thereof.In an embodiment, the present composition includes about 1 or more partsof medium chain peroxycarboxylic acid for each 4 parts of short chaincarboxylic acid, short chain peroxycarboxylic acid, or mixture thereof.In an embodiment, the present composition includes about 1 or more partsof medium chain peroxycarboxylic acid for each 3 parts of short chaincarboxylic acid, short chain peroxycarboxylic acid, or mixture thereof.In an embodiment, the present composition includes about 1 or more partsof medium chain peroxycarboxylic acid for each 2 parts of short chaincarboxylic acid, short chain peroxycarboxylic acid, or mixture thereof.In an embodiment, the present composition includes about 1 or more partsof medium chain peroxycarboxylic acid for each 1 part of short chaincarboxylic acid, short chain peroxycarboxylic acid, or mixture thereof.

In an embodiment, the present composition has an odor less unpleasantthan (e.g., as measured by an hedonic tone rating) than 5, 4, 3, 2, or 1wt-% acetic acid in water. In an embodiment, the present composition hasan odor less unpleasant than (e.g., as measured by an hedonic tonerating) than 5 wt-% acetic acid in water. In an embodiment, the presentcomposition has an odor less unpleasant than (e.g., as measured by anhedonic tone rating) than 4 wt-% acetic acid in water. In an embodiment,the present composition has an odor less unpleasant than (e.g., asmeasured by an hedonic tone rating) than 3 wt-% acetic acid in water. Inan embodiment, the present composition has an odor less unpleasant than(e.g., as measured by an hedonic tone rating) than 2 wt-% acetic acid inwater. In an embodiment, the present composition has an odor with anodor less unpleasant than (e.g., as measured by an hedonic tone rating)than 1 wt-% acetic acid in water.

In certain embodiments, the present composition includes one or more(e.g., at least one) of oxidizing agent, acidulant, stabilizing agent,mixtures thereof, or the like. The present composition can include anyof a variety of oxidizing agents, for example, hydrogen peroxide. Theoxidizing agent can be effective to convert a medium chain carboxylicacid to a medium chain peroxycarboxylic acid. The oxidizing agent canalso have antimicrobial activity, although it may not be present at aconcentration sufficient to exhibit such activity. The presentcomposition can include any of a variety of acidulants, for example, aninorganic acid. The acidulant can be effective to bring the pH of thepresent concentrate composition to less than 1, or to bring the pH ofthe present use composition to about 5 or below, about 4 or below, orabout 3 or below. The acidulant can augment the antimicrobial activityof the present composition. The present composition can include any of avariety of stabilizing agents, for example, sequestrant, for example,phosphonate sequestrant. The sequestrant can be effective to stabilizethe peroxycarboxylic acid.

In an embodiment, the present composition exhibits advantageousstability of the peroxycarboxylic acid. It is believed that inapproximately one year at ambient conditions or room temperature (or 1week at 60° C.) the amount of peroxycarboxylic acid in the compositionscan be about 80% or more, about 85% or more, about 90% or more, or about95% or more of the initial values or use composition levels. Such agedcompositions are included in the scope of the present invention.

In an embodiment, the present composition exhibits advantageous efficacycompared to other antimicrobial compositions at the same level ofactive. In certain embodiments, the present composition has reduced orno volatile organic compounds compared to conventional peroxycarboxylicacid compositions. In an embodiment, the present composition has ahigher flash point compared to conventional peroxycarboxylic acidcompositions. In an embodiment, the present composition exhibitsimproved operator or user safety compared to conventionalperoxycarboxylic acid compositions. In an embodiment, the presentcomposition exhibits improved storage or transportation safety comparedto conventional peroxycarboxylic acid compositions.

In certain embodiments, the present composition includes about 0.0005 toabout 5 wt-% medium chain peroxycarboxylic acid, about 0.3 to about 7wt-% medium chain peroxycarboxylic acid, about 0.5 to about 5 wt-%medium chain peroxycarboxylic acid, about 0.5 to about 4 wt-% mediumchain peroxycarboxylic acid, about 0.8 to about 3 wt-% medium chainperoxycarboxylic acid, about 1 to about 3 wt-% medium chainperoxycarboxylic acid, or about 1 to about 2 wt-% medium chainperoxycarboxylic acid. The composition can include any of these rangesor amounts not modified by about.

In certain embodiments, the present composition includes about 0.001 toabout 8 wt-% medium chain carboxylic acid, about 1 to about 10 wt-%medium chain carboxylic acid, about 1 to about 8 wt-% medium chaincarboxylic acid, about 1.5 to about 6 wt-% medium chain carboxylic acid,about 2 to about 8 wt-% medium chain carboxylic acid, about 2 to about 6wt-% medium chain carboxylic acid, about 2 to about 4 wt-% medium chaincarboxylic acid, about 2.5 to about 5 wt-% medium chain carboxylic acid,about 3 to about 6 wt-% medium chain carboxylic acid, or about 3 toabout 5 wt-% medium chain carboxylic acid. The composition can includeany of these ranges or amounts not modified by about.

In certain embodiments, the present composition includes about 0 toabout 98 wt-% carrier, about 0.001 to about 99.99 wt-% carrier, about0.2 to about 60 wt-% carrier, about 1 to about 98 wt-% carrier, about 5to about 99.99 wt-% carrier, about 5 to about 97 wt-% carrier, about 5to about 90 wt-% carrier, about 5 to about 70 wt-% carrier, about 5 toabout 20 wt-% carrier, about 10 to about 90 wt-% carrier, about 10 toabout 80 wt-% carrier, about 10 to about 50 wt-% carrier, about 10 toabout 20 wt-% carrier, about 15 to about 70 wt-% carrier, about 15 toabout 80 wt-% carrier, about 20 to about 70 wt-% carrier, about 20 toabout 50 wt-% carrier, about 20 to about 40 wt-% carrier, about 20 toabout 30 wt-% carrier, about 30 to about 75 wt-% carrier, about 30 toabout 70 wt-% carrier, about 40 to about 99.99 wt-% carrier, about 40 toabout 90 wt-% carrier, or about 60 to about 70 wt-% carrier. Thecomposition can include any of these ranges or amounts not modified byabout.

In certain embodiments, the present composition includes about 0.001 toabout 80 wt-% solubilizer, about 0.001 to about 60 wt-% solubilizer,about 1 to about 80 wt-% solubilizer, about 1 to about 25 wt-%solubilizer, about 1 to about 20 wt-% solubilizer, about 2 to about 70wt-% solubilizer, about 2 to about 60 wt-% solubilizer, about 2 to about20 wt-% solubilizer, about 3 to about 65 wt-% solubilizer, about 3 toabout 15 wt-% solubilizer, about 4 to about 10 wt-% solubilizer, about 4to about 20 wt-% solubilizer, about 5 to about 70 wt-% solubilizer,about 5 to about 60 wt-% solubilizer, about 5 to about 20 wt-%solubilizer, about 10 to about 70 wt-% solubilizer, about 10 to about 65wt-% solubilizer, about 10 to about 20 wt-% solubilizer, about 20 toabout 60 wt-% solubilizer, or about 40 to about 60 wt-% solubilizer. Thecomposition can include any of these ranges or amounts not modified byabout.

In certain embodiments, the present composition includes about 0.001 toabout 30 wt-% oxidizing agent, about 0.001 to about 10 wt-% oxidizingagent, 0.002 to about 10 wt-% oxidizing agent, about 2 to about 30 wt-%oxidizing agent, about 2 to about 25 wt-% oxidizing agent, about 2 toabout 20 wt-% oxidizing agent, about 4 to about 20 wt-% oxidizing agent,about 5 to about 10 wt-% oxidizing agent, or about 6 to about 10 wt-%oxidizing agent. The composition can include any of these ranges oramounts not modified by about.

In certain embodiments, the present composition includes about 0.001 toabout 50 wt-% acidulant, about 0.001 to about 30 wt-% acidulant, about 1to about 50 wt-% acidulant, about 1 to about 30 wt-% acidulant, about 2to about 40 wt-% acidulant, about 2 to about 10 wt-% acidulant, about 3to about 40 wt-% acidulant, about 5 to about 40 wt-% acidulant, about 5to about 25 wt-% acidulant, about 10 to about 40 wt-% acidulant, about10 to about 30 wt-% acidulant, about 15 to about 35 wt-% acidulant,about 15 to about 30 wt-% acidulant, or about 40 to about 60 wt-%acidulant. The composition can include any of these ranges or amountsnot modified by about.

In certain embodiments, the present composition includes about 0.001 toabout 50 wt-% stabilizing agent, about 0.001 to about 5 wt-% stabilizingagent, about 0.5 to about 50 wt-% stabilizing agent, about 1 to about 50wt-% stabilizing agent, about 1 to about 30 wt-% stabilizing agent,about 1 to about 10 wt-% stabilizing agent, about 1 to about 5 wt-%stabilizing agent, about 1 to about 3 wt-% stabilizing agent, about 2 toabout 10 wt-% stabilizing agent, about 2 to about 5 wt-% stabilizingagent, or about 5 to about 15 wt-% stabilizing agent. The compositioncan include any of these ranges or amounts not modified by about.

Compositions of Medium Chain Carboxylic Acids and/or PeroxycarboxylicAcids

Peroxycarboxylic (or percarboxylic) acids generally have the formulaR(CO₃H)_(n), where, for example, R is an alkyl, arylalkyl, cycloalkyl,aromatic, or heterocyclic group, and n is one, two, or three, and namedby prefixing the parent acid with peroxy. The R group can be saturatedor unsaturated as well as substituted or unsubstituted. The compositionand methods of the invention can employ medium chain peroxycarboxylicacids containing, for example, 6 to 12 carbon atoms. For example, mediumchain peroxycarboxylic (or percarboxylic) acids can have the formulaR(CO₃H)_(n), where R is a C₅-C₁₁ alkyl group, a C₅-C₁₁ cycloalkyl, aC₅-C₁₁ arylalkyl group, C₅-C₁₁ aryl group, or a C₅-C₁₁ heterocyclicgroup; and n is one, two, or three.

Peroxycarboxylic acids can be made by the direct action of an oxidizingagent on a carboxylic acid, by autoxidation of aldehydes, or from acidchlorides, and hydrides, or carboxylic anhydrides with hydrogen orsodium peroxide. In an embodiment, the medium chain percarboxylic acidscan be made by the direct, acid catalyzed equilibrium action of hydrogenperoxide on the medium chain carboxylic acid. Scheme 1 illustrates anequilibrium between carboxylic acid and oxidizing agent (Ox) on one sideand peroxycarboxylic acid and reduced oxidizing agent (OX_(red)) on theother:RCOOH+Ox≈RCOOOH+Ox_(red)  (1)Scheme 2 illustrates an embodiment of the equilibrium of scheme 1 inwhich the oxidizing agent is hydrogen peroxide on one side andperoxycarboxylic acid and water on the other:RCOOH+H₂O₂≈RCOOOH+H₂O  (2)In conventional mixed peroxycarboxylic acid compositions it is believedthat the equilibrium constant for the reaction illustrated in scheme 2is about 2.5, which may reflect the equilibrium for acetic acid.Although not limiting to the present invention, it is believed that thepresent compositions have an equilibrium constant of about 4.

Peroxycarboxylic acids useful in the compositions and methods of thepresent invention include peroxypentanoic, peroxyhexanoic,peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic,peroxyundecanoic, peroxydodecanoic, peroxyascorbic, peroxyadipic,peroxycitric, peroxypimelic, or peroxysuberic acid, mixtures thereof, orthe like. The alkyl backbones of these medium chain peroxycarboxylicacids can be straight chain, branched, or a mixture thereof. Peroxyforms of carboxylic acids with more than one carboxylate moiety can haveone or more (e.g., at least one) of the carboxyl moieties present asperoxycarboxyl moieties.

Peroxyoctanoic (or peroctanoic) acid is a peroxycarboxylic acid havingthe formula, for example, of n-peroxyoctanoic acid: CH₃(CH₂)₆COOOH.Peroxyoctanoic acid can be an acid with a straight chain alkyl moiety,an acid with a branched alkyl moiety, or a mixture thereof.Peroxyoctanoic acid is surface active and can assist in wettinghydrophobic surfaces, such as those of microbes.

The composition of the present invention can include a carboxylic acid.Generally, carboxylic acids have the formula R—COOH wherein the R canrepresent any number of different groups including aliphatic groups,alicyclic groups, aromatic groups, heterocyclic groups, all of which canbe saturated or unsaturated as well as substituted or unsubstituted.Carboxylic acids can have one, two, three, or more carboxyl groups. Thecomposition and methods of the invention typically employ medium chaincarboxylic acids containing, for example, 6 to 12 carbon atoms. Forexample, medium chain carboxylic acids can have the formula R—COOH inwhich R can be a C₅-C₁₁ alkyl group, a C₅-C₁₁ cycloalkyl group, a C₅-C₁₁arylalkyl group, C₅-C₁₁ aryl group, or a C₅-C₁₁ heterocyclic group.

Suitable medium chain carboxylic acids include pentanoic, hexanoic,heptanoic, octanoic, nonanoic, decanoic, undecanoic, dodecanoic,ascorbic, citric, adipic, pimelic, and suberic acid. The alkyl backbonesof these medium chain carboxylic acids can be straight chain, branched,or a mixture thereof. Carboxylic acids which are generally useful arethose having one or two carboxyl groups where the R group is a primaryalkyl chain having a length of C₄ to C₁₁. The primary alkyl chain isthat carbon chain of the molecule having the greatest length of carbonatoms and directly appending carboxyl functional groups.

The present compositions and methods include a medium chainperoxycarboxylic acid. The medium chain peroxycarboxylic acid caninclude or be a C6 to C12 peroxycarboxylic acid. The C6 to C12peroxycarboxylic acid can include or be peroxyhexanoic acid,peroxyheptanoic acid, peroxyoctanoic acid, peroxynonanoic acid,peroxydecanoic acid, peroxyundecanoic acid, peroxydodecanoic acid, ormixture thereof. The medium chain peroxycarboxylic acid can include orbe a C7 to C12 peroxycarboxylic acid. The C7 to C12 peroxycarboxylicacid can include or be peroxyheptanoic acid, peroxyoctanoic acid,peroxynonanoic acid, peroxydecanoic acid, peroxyundecanoic acid,peroxydodecanoic acid, or mixture thereof. The medium chainperoxycarboxylic acid can include or be a C6 to C10 peroxycarboxylicacid. The C6 to C10 peroxycarboxylic acid can include or beperoxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoic acid,peroxynonanoic acid, peroxydecanoic acid, or mixture thereof. The mediumchain peroxycarboxylic acid can include or be a C8 to C10peroxycarboxylic acid. The C8 to C10 peroxycarboxylic acid can includeor be peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, ormixture thereof. In certain embodiments, the medium chain peroxyoctanoicacid includes or is peroxyoctanoic acid, peroxydecanoic acid, or mixturethereof. In an embodiment, the medium chain peroxycarboxylic acidincludes or is peroxyoctanoic acid.

In certain embodiments, the present composition includes about 0.0005 toabout 5 wt-% medium chain peroxycarboxylic acid, about 0.3 to about 7wt-% medium chain peroxycarboxylic acid, about 0.5 to about 5 wt-%medium chain peroxycarboxylic acid, about 0.5 to about 4 wt-% mediumchain peroxycarboxylic acid, about 0.8 to about 3 wt-% medium chainperoxycarboxylic acid, about 1 to about 3 wt-% medium chainperoxycarboxylic acid, or about 1 to about 2 wt-% medium chainperoxycarboxylic acid. The composition can include any of these rangesor amounts not modified by about.

In an embodiment, the present compositions and methods include a mediumchain carboxylic acid. The medium chain carboxylic acid can include orbe a C6 to C12 carboxylic acid. The C6 to C12 carboxylic acid caninclude or be hexanoic acid, heptanoic acid, octanoic acid, nonanoicacid, decanoic acid, undecanoic acid, dodecanoic acid, or mixturethereof. The medium chain carboxylic acid can include or be a C7 to C12carboxylic acid. The C7 to C12 carboxylic acid can include or beheptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoicacid, dodecanoic acid, or mixture thereof. The medium chainperoxycarboxylic acid can include or be a C6 to C10 carboxylic acid. TheC6 to C10 carboxylic acid can include or be hexanoic acid, heptanoicacid, octanoic acid, nonanoic acid, decanoic acid, or mixture thereof.The medium chain carboxylic acid can include or be a C8 to C10carboxylic acid. The C8 to C10 carboxylic acid can include or beoctanoic acid, nonanoic acid, decanoic acid, or mixture thereof. Incertain embodiments, the medium chain carboxylic acid includes or isoctanoic acid, decanoic acid, or mixture thereof. In an embodiment, themedium chain carboxylic acid includes or is octanoic acid.

In certain embodiments, the present composition includes about 0.001 toabout 8 wt-% medium chain carboxylic acid, about 1 to about 10 wt-%medium chain carboxylic acid, about 1 to about 8 wt-% medium chaincarboxylic acid, about 1.5 to about 6 wt-% medium chain carboxylic acid,about 2 to about 8 wt-% medium chain carboxylic acid, about 2 to about 6wt-% medium chain carboxylic acid, about 2 to about 4 wt-% medium chaincarboxylic acid, about 2.5 to about 5 wt-% medium chain carboxylic acid,about 3 to about 6 wt-% medium chain carboxylic acid, or about 3 toabout 5 wt-% medium chain carboxylic acid. The composition can includeany of these ranges or amounts not modified by about.

In an embodiment, the compositions and methods include a medium chainperoxycarboxylic acid and the corresponding medium chain carboxylicacid.

In an embodiment, the present composition includes an amount of mediumchain peroxycarboxylic acid effective for killing one or more (e.g., atleast one) of the food-borne pathogenic bacteria associated with a foodproduct, such as Salmonella typhimurium, Salmonella javiana,Campylobacter jejuni, Listeria monocytogenes, and Escherichia coliO157:H7, yeast, mold, and the like. In an embodiment, the presentcomposition includes an amount of medium chain peroxycarboxylic acideffective for killing one or more (e.g., at least one) of the pathogenicbacteria associated with a health care surfaces and environments, suchas Salmonella typhimurium, Staphylococcus aureus, Salmonellacholeraesurus, Pseudomonas aeruginosa, Escherichia coli, mycobacteria,yeast, mold, and the like. The compositions and methods of the presentinvention have activity against a wide variety of microorganisms such asGram positive (for example, Listeria monocytogenes or Staphylococcusaureus) and Gram negative (for example, Escherichia coli or Pseudomonasaeruginosa) bacteria, yeast, molds, bacterial spores, viruses, etc. Thecompositions and methods of the present invention, as described above,have activity against a wide variety of human pathogens. The presentcompositions and methods can kill a wide variety of microorganisms on afood processing surface, on the surface of a food product, in water usedfor washing or processing of food product, on a health care surface, orin a health care environment.

Embodiments of the present invention include medium chain carboxylicacid and medium chain peroxycarboxylic acid, and certain embodimentsspecifically exclude short chain peroxycarboxylic acid, short chaincarboxylic acid, or mixture thereof. Nonetheless embodiments of thepresent compositions can include short chain peroxycarboxylic acid,short chain carboxylic acid, or mixture thereof. It is not intended thataddition of short chain peroxycarboxylic acid, short chain carboxylicacid, or mixture thereof to a composition should necessarily take acomposition outside the spirit and scope of the present invention.

Solubilizers

The present compositions can include a solubilizer. The presentinvention relates to solubilizers for medium chain carboxylic acids andmedium chain peroxycarboxylic acids. In an embodiment, the solubilizercan increase or maintain the solubility in the composition of the mediumchain peroxycarboxylic acid or the medium chain carboxylic acid. Thepresent compositions and methods can include any of a variety ofsuitable solubilizers. For example, the solubilizer can include asolvent, a surfactant, or a mixture thereof. In an embodiment, thesurfactant can be employed as a solvent. In an embodiment, thesurfactant can form a microemulsion. In an embodiment, the compositionincluding the present solubilizer takes the form of a viscoelastic gelor liquid. In an embodiment, the solubilizer is effective to dissolveoctanoic acid at a concentration of 5 wt-% in water. In an embodiment,the solubilizer is effective to dissolve octanoic acid at aconcentration of 4 wt-% in water. In an embodiment, the solubilizer iseffective to dissolve octanoic acid at a concentration of 3 wt-% inwater. In an embodiment, the solubilizer is effective to dissolveoctanoic acid at a concentration of 2 wt-% in water.

In certain embodiments, the present composition includes about 0.001 toabout 80 wt-% solubilizer, about 0.001 to about 60 wt-% solubilizer,about 1 to about 80 wt-% solubilizer, about 1 to about 25 wt-%solubilizer, about 1 to about 20 wt-% solubilizer, about 2 to about 70wt-% solubilizer, about 2 to about 60 wt-% solubilizer, about 2 to about20 wt-% solubilizer, about 3 to about 65 wt-% solubilizer, about 3 toabout 15 wt-% solubilizer, about 4 to about 10 wt-% solubilizer, about 4to about 20 wt-% solubilizer, about 5 to about 70 wt-% solubilizer,about 5 to about 60 wt-% solubilizer, about 5 to about 20 wt-%solubilizer, about 10 to about 70 wt-% solubilizer, about 10 to about 65wt-% solubilizer, about 10 to about 20 wt-% solubilizer, about 20 toabout 60 wt-% solubilizer, or about 40 to about 60 wt-% solubilizer. Thecomposition can include any of these ranges or amounts not modified byabout.

Solvent Solubilizers and Compositions Including Them

In an embodiment, the present compositions and methods can include assolubilizer one or more (e.g., at least one) solvents. Suitable solventsinclude any of a variety of solvents that solubilize but do notsignificantly degrade the medium chain peroxycarboxylic acid. Suitablesolvents include polyalkylene oxide, capped polyalkylene oxide, glycolether, nonionic surfactant, mixtures thereof, or the like.

In an embodiment, the present composition includes medium chainperoxycarboxylic acid; medium chain carboxylic acid; carrier; andpolyalkylene oxide, capped polyalkylene oxide, nonionic surfactant, ormixture thereof. For example, the present composition can include about0.5 to about 5 wt-% medium chain peroxycarboxylic acid; about 1 to about10 wt-% medium chain carboxylic acid; about 1 to about 98 wt-% carrier;and about 1 to about 80 wt-% polyalkylene oxide, capped polyalkyleneoxide, nonionic surfactant, or mixture thereof. For example, the presentcomposition can include about 0.5 to about 5 wt-% medium chainperoxycarboxylic acid; about 1 to about 10 wt-% medium chain carboxylicacid; about 5 to about 35 wt-% carrier; and about 20 to about 65 wt-%polyalkylene oxide, capped polyalkylene oxide, nonionic surfactant, ormixture thereof. For example, the present composition can include about0.5 to about 5 wt-% medium chain peroxycarboxylic acid; about 1 to about10 wt-% medium chain carboxylic acid; about 10 to about 35 wt-% carrier;and about 40 to about 60 wt-% polyalkylene oxide, capped polyalkyleneoxide, nonionic surfactant, or mixture thereof. In an embodiment, thepresent composition includes solvent solubilizer and less than or equalto 35 wt-% carrier (e.g., water). The composition can include any ofthese ranges or amounts not modified by about.

In an embodiment, the present composition includes C8 peroxycarboxylicacid; C8 carboxylic acid; water; and polyalkylene oxide, cappedpolyalkylene oxide, nonionic surfactant, or mixture thereof. Forexample, the present composition can include about 0.5 to about 5 wt-%C8 peroxycarboxylic acid; about 1 to about 10 wt-% C8 carboxylic acid;about 1 to about 98 wt-% water; and about 1 to about 80 wt-%polyalkylene oxide, capped polyalkylene oxide, nonionic surfactant, ormixture thereof. For example, the present composition can include about0.5 to about 5 wt-% C8 peroxycarboxylic acid; about 1 to about 10 wt-%C8 carboxylic acid; about 5 to about 35 wt-% water; and about 20 toabout 65 wt-% polyalkylene oxide, capped polyalkylene oxide, nonionicsurfactant, or mixture thereof. For example, the present composition caninclude about 0.5 to about 5 wt-% C8 peroxycarboxylic acid; about 1 toabout 10 wt-% C8 carboxylic acid; about 10 to about 35 wt-% water; andabout 40 to about 60 wt-% polyalkylene oxide, capped polyalkylene oxide,nonionic surfactant, or mixture thereof. The composition can include anyof these ranges or amounts not modified by about.

In certain embodiments, the present composition includes about 0.001 toabout 80 wt-% solvent as solubilizer, about 0.001 to about 60 wt-%solvent as solubilizer, about 1 to about 80 wt-% solvent as solubilizer,about 5 to about 70 wt-% solvent as solubilizer, about 10 to about 65wt-% solvent as solubilizer, or about 20 to about 60 wt-% solvent assolubilizer. The composition can include any of these ranges or amountsnot modified by about.

In an embodiment, when the present compositions and methods include asolvent as solubilizer, they need not include a significant amount, oreven any, of a short chain peroxycarboxylic acid, a short chaincarboxylic acid, or a mixture thereof. Examples of short chaincarboxylic acids include formic acid, acetic acid, propionic acid, andbutanoic acid. Short chain carboxylic acids and peroxycarboxylic acidsinclude those with 4 or fewer carbon atoms. In an embodiment, thepresent compositions and methods including a solvent solubilizer neednot include substantial amounts of short chain peroxycarboxylic acid. Inan embodiment, the present compositions and methods including a solventsolubilizer can be free of added short chain peroxycarboxylic acid.

In an embodiment, the present compositions and methods including asolvent solubilizer can include medium chain peroxycarboxylic acid ingreater proportion compared to the short chain peroxycarboxylic acidthan found in conventional compositions. For example, the presentcompositions and methods can include solvent solubilizer and about 1 ormore parts of medium chain peroxycarboxylic acid for each 8 parts ofshort chain carboxylic acid, short chain peroxycarboxylic acid, ormixture thereof. For example, the present compositions and methods caninclude solvent solubilizer and short chain carboxylic acid, short chainperoxycarboxylic acid, or mixture thereof at a level insufficient tocause odor offensive to a typical person.

Polyalkylene Oxide Solubilizers

Suitable polyalkylene oxides include polyethylene glycol, polypropyleneglycol, polybutylene glycol, mixtures thereof, or the like. Suitablecapped polyalkylene oxides include mono-alkyl and di-alkyl ethers of therespective polyalkylene oxides, such as mono- and di-methyl ethers ofpolyalkylene glycol, mono- and di-ethyl ethers of polyalkylene glycol,mono- and di-propyl ethers of polyalkylene glycol, mono- and di-butylethers of polyalkylene glycol, mixtures thereof, or the like. Suitablecapped polyalkylene oxides include methyl polyethylene glycol (e.g., themonomethyl ether of polyethylene glycol), dimethyl polyethylene glycol(e.g., the dimethyl ether of polyethylene glycol), mixtures thereof, orthe like.

Glycol Ether Solubilizers

Suitable solvent solubilizers include glycol ethers. Suitable glycolethers include diethylene glycol n-butyl ether, diethylene glycoln-propyl ether, diethylene glycol ethyl ether, diethylene glycol methylether, diethylene glycol t-butyl ether, dipropylene glycol n-butylether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether,dipropylene glycol propyl ether, dipropylene glycol tert-butyl ether,ethylene glycol butyl ether, ethylene glycol propyl ether, ethyleneglycol ethyl ether, ethylene glycol methyl ether, ethylene glycol methylether acetate, propylene glycol n-butyl ether, propylene glycol ethylether, propylene glycol methyl ether, propylene glycol n-propyl ether,tripropylene glycol methyl ether and tripropylene glycol n-butyl ether,ethylene glycol phenyl ether (commercially available as DOWANOL EPH™from Dow Chemical Co.), propylene glycol phenyl ether (commerciallyavailable as DOWANOL PPH™ from Dow Chemical Co.), and the like, ormixtures thereof. Additional suitable commercially available glycolethers (all of which are available from Union Carbide Corp.) includeButoxyethyl PROPASOL™, Butyl CARBITOL™ acetate, Butyl CARBITOL™, ButylCELLOSOLVE™ acetate, Butyl CELLOSOLVE™, Butyl DIPROPASOL™, ButylPROPASOL™, CARBITOL™ PM-600, CARBITOL™ Low Gravity, CELLOSOLVE™ acetate,CELLOSOLVE™, Ester EEP™, FILMER IBT™, Hexyl CARBITOL™, HexylCELLOSOLVE™, Methyl CARBITOL™, Methyl CELLOSOLVE™ acetate, MethylCELLOSOLVE™, Methyl DIPROPASOL™, Methyl PROPASOL™ acetate, MethylPROPASOL™, Propyl CARBITOL™, Propyl CELLOSOLVE™, Propyl DIPROPASOL™ andPropyl PROPASOL™.

Nonionic Surfactants

Suitable nonionic surfactants for use as solvents include alkoxylatedsurfactants. Suitable alkoxylated surfactants include EO/PO copolymers,capped EO/PO copolymers, alcohol alkoxylates, capped alcoholalkoxylates, mixtures thereof, or the like. Suitable alkoxylatedsurfactants for use as solvents include EO/PO block copolymers, such asthe Pluronic and reverse Pluronic surfactants; alcohol alkoxylates, suchas Dehypon LS-54 (R-(EO)₅(PO)₄) and Dehypon LS-36 (R-(EO)₃(PO)₆); andcapped alcohol alkoxylates, such as Plurafac LF221 and Tegoten EC11;mixtures thereof, or the like. When employed as a solvent a surfactant,such as a nonionic surfactant, can be at concentrations higher thanthose conventionally employed as surfactant.

Semi-Polar Nonionic Surfactants

The semi-polar type of nonionic surface active agents are another classof nonionic surfactant useful in compositions of the present invention.Semi-polar nonionic surfactants include the amine oxides, phosphineoxides, sulfoxides and their alkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxyalkyl of 1-3 carbon atoms or amixture thereof; R² and R³ can be attached to each other, e.g. throughan oxygen or nitrogen atom, to form a ring structure; R⁴ is an alkyleneor a hydroxyalkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20.

Useful water soluble amine oxide surfactants are selected from theoctyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(loweralkyl) anine oxides, specific examples of which are octyldimethylamineoxide, nonyldimethylamine oxide, decyldimethylamine oxide,undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylanine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Surfactant Solubilizers and Compositions Including Them

In an embodiment, the present compositions and methods can include assolubilizer one or more (e.g., at least one) surfactants, e.g., amicroemulsion forming surfactant. Suitable surfactants include anionicsurfactant, cationic surfactant, amphoteric surfactant, zwitterionicsurfactant, mixtures thereof, or the like. Suitable microemulsionforming surfactants include anionic surfactant, cationic surfactant,amphoteric surfactant, zwitterionic surfactant, mixtures thereof, or thelike. Suitable microemulsion forming surfactants include anionicsurfactant. A microemulsion forming surfactant can form a microemulsionin a composition including a medium chain peroxycarboxylic acid, amedium chain carboxylic acid, or a mixture thereof. In an embodiment,the present composition includes a microemulsion.

In an embodiment, the present composition can be determined to be amicroemulsion by testing the composition for being a shear thinningviscoelastic gel or liquid that has a blue tyndall appearance. Althoughnot limiting to the present invention, blue tyndall appearance isbelieved to indicate a heterogeneous system of a small, suspendeddispersion (e.g., a microemulsion), which is effective in scatteringblue light.

In an embodiment, the present composition can be determined to be amicroemulsion by testing the ability to form a physically stablecomposition at different concentrations of surfactant solubilizer. Amicroemulsion can yield a curve with a maximum of physical stability ata concentration with unstable compositions at higher and lowerconcentrations. Typically, mixtures of solvents and surfactants (e.g.,acetic acid and surfactant) do not form microemulsions.

In an embodiment, the composition including surfactant solubilizer takesthe form of a viscoelastic gel or liquid. Increasing the concentrationof the medium chain carboxylic acid, medium chain peroxycarboxylic acid,or mixture thereof can increase the degree to which the composition is aviscoelastic gel or liquid. Increasing the concentration of thesurfactant solubilizer can increase the degree to which the compositionis a viscoelastic gel or liquid. In an embodiment, the gel can besufficiently viscoelastic to hold its molded shape. Alkyl benzenesulfonate surfactant (e.g., LAS) can be employed to form a viscoelasticgel or liquid that can hold its molded shape. In an embodiment, thealkyl benzene sulfonate surfactant containing viscoelastic gel can holdits shape even at 60° C.

Although not limiting to the present invention, the present compositionsmay include medium chain peroxycarboxylic acid sequestered in thesurfactant of the microemulsion. This can stabilize the peroxycarboxylicacid by keeping it away from impurities or reducing agents in the bulkwater. This can increase the production of peroxycarboxylic acid bypulling it out of solution. Although not limiting to the presentinvention, it is believed that one explanation for the viscoelasticproperties of gels of the present compositions is that they are due torepulsive forces between the dispersions/droplets that are stabilized bythe microemulsion-forming surfactant. Surfactants that are charged mayincrease the electrostatic repulsion. Suitable charged surfactantsinclude anionic surfactants.

In an embodiment, the present composition includes anionic surfactantand another surfactant or surfactants. For example, the presentcompositions can include anionic surfactant and nonionic surfactant orsemi-polar nonionic surfactant. For example, the present compositionscan include anionic surfactant and alkyl amine oxide or alkyl dimethylamine.

In an embodiment, the present composition includes medium chainperoxycarboxylic acid; medium chain carboxylic acid; carrier; and one ormore (e.g., at least one) surfactants, e.g., microemulsion formingsurfactants. For example, the present composition can include about 0.5to about 5 wt-% medium chain peroxycarboxylic acid; about 1 to about 10wt-% medium chain carboxylic acid; about 5 to about 97 wt-% carrier; andabout 1 to about 20 wt-% surfactant, e.g., microemulsion formingsurfactant. For example, the present composition can include about 0.5to about 5 wt-% medium chain peroxycarboxylic acid; about 1 to about 10wt-% medium chain carboxylic acid; about 15 to about 80 wt-% carrier;and about 1 to about 20 wt-% surfactant, e.g., microemulsion formingsurfactant. For example, the present composition can include about 0.5to about 5 wt-% medium chain peroxycarboxylic acid; about 1 to about 10wt-% medium chain carboxylic acid; about 30 to about 70 wt-% carrier;and about 2 to about 20 wt-% surfactant, e.g., microemulsion formingsurfactant. In an embodiment, the present composition includessurfactant or microemulsion former solubilizer and greater than or equalto 35 wt-% carrier (e.g., water). The composition can include any ofthese ranges or amounts not modified by about.

In an embodiment, the present composition includes C8 peroxycarboxylicacid; C8 carboxylic acid; water; and one or more (e.g., at least one)surfactants, e.g., microemulsion forming surfactants. For example, thepresent composition can include about 0.5 to about 5 wt-% C8peroxycarboxylic acid; about 1 to about 10 wt-% C8 carboxylic acid;about 5 to about 97 wt-% water; and about 1 to about 20 wt-% surfactant,e.g., microemulsion forming surfactant. For example, the presentcomposition can include about 0.5 to about 5 wt-% C8 peroxycarboxylicacid; about 1 to about 10 wt-% C8 carboxylic acid; about 15 to about 80wt-% water; and about 1 to about 20 wt-% surfactant, e.g., microemulsionforming surfactant. For example, the present composition can includeabout 0.5 to about 5 wt-% C8 peroxycarboxylic acid; about 1 to about 10wt-% C8 carboxylic acid; about 30 to about 70 wt-% water; and about 2 toabout 20 wt-% surfactant, e.g., microemulsion forming surfactant. Thecomposition can include any of these ranges or amounts not modified byabout.

In certain embodiments, the present composition includes about 0.001 toabout 60 wt-% surfactant, e.g., microemulsion forming surfactant, assolubilizer, about 1 to about 25 wt-% surfactant, e.g., microemulsionforming surfactant, as solubilizer, about 1 to about 20 wt-% surfactant,e.g., microemulsion forming surfactant, as solubilizer, about 2 to about20 wt-% surfactant, e.g., microemulsion forming surfactant, assolubilizer, about 3 to about 15 wt-% surfactant, e.g., microemulsionform ing surfactant, as solubilizer, about 4 to about 20 wt-%surfactant, e.g., microemulsion forming surfactant, as solubilizer,about 4 to about 10 wt-% surfactant, e.g., microemulsion formingsurfactant, as solubilizer, about 5 to about 20 wt-% surfactant, e.g.,microemulsion forming surfactant, as solubilizer, or about 10 to about20 wt-% surfactant, e.g., microemulsion forming surfactant, assolubilizer. The composition can include any of these ranges or amountsnot modified by about.

Anionic Surfactants

The present composition can include an anionic surfactant assolubilizer. Suitable anionic surfactants include organic sulfonatesurfactant, organic sulfate surfactant, phosphate ester surfactant,carboxylate surfactant, mixtures thereof, or the like. In an embodiment,the anionic surfactant includes alkyl sulfonate, alkylaryl sulfonate,alkylated diphenyl oxide disulfonate, alkylated naphthalene sulfonate,alcohol alkoxylate carboxylate, sarcosinate, taurate, acyl amino acid,alkanoic ester, phosphate ester, sulfuric acid ester, salt or acid formthereof, or mixture thereof. The particular salts will be suitablyselected depending upon the particular formulation and the needstherein.

Suitable anionic surfactants include sulfonic acids (and salts), such asisethionates (e.g. acyl isethionates), alkylaryl sulfonic acids andsalts thereof, alkyl sulfonates, secondary alkane sulfonates, and thelike.

Examples of suitable synthetic, water soluble anionic detergentcompounds include the ammonium and substituted ammonium (such as mono-,di- and triethanolamine) and alkali metal (such as sodium, lithium andpotassium) salts of the alkyl mononuclear aromatic sulfonates such asthe alkyl benzene sulfonates containing from about 5 to about 18 carbonatoms in the alkyl group in a straight or branched chain, e.g., thesalts of alkyl benzene sulfonates or of alkyl toluene, xylene, cumeneand phenol sulfonates; alkyl naphthalene sulfonate, diamyl naphthalenesulfonate, and dinonyl naphthalene sulfonate and alkoxylated derivativesor their free acids. Suitable sulfonates include olefin sulfonates, suchas long chain alkene sulfonates, long chain hydroxyalkane sulfonates ormixtures of alkenesulfonates and hydroxyalkane-sulfonates. Suitablesulfonates include secondary alkane sulfonates.

In certain embodiments, the present compositions including an anionicsurfactant, such as a normal C8 sulfonate, can be non-foam or low foamcompositions. Such compositions can be advantageous for applicationssuch as clean in place, machine warewashing, destaining, and sanitizing,laundry washing, destaining, and sanitizing, etc.

For applications in which foaming is desirable, a foaming agent can beadded as part of the present composition or separately. In a two-stepoffering, a foaming agent can be combined with a dilution of thenon-foam or low foam composition to form a foaming use solution. In aone-step offering, the foaming agent can be incorporated into theconcentrated composition. One suitable foaming agent is LAS acid. LASacid can form a microemulsion in the present compositions. LAS acid canform a viscoelastic gel or liquid in the present compositions.Additional suitable foaming agents include secondary alkane sulfonate,alkylated diphenyl oxide disulfonate (e.g., C12 alkyl diphenyl oxidedisulfonate), alkyl ether sulfate (e.g., with n=1-3) (e.g., sodiumlaureth sulfate (with n=1, 2, or 3)), sodium lauryl sulfate, or thelike.

In an embodiment, such foaming agents provide a foaming composition withone or more desirable foaming characteristics. Desirable foamingcharacteristics include, for example, foam being visible for about 5 minafter forming the foam; foam with continuous and good drainage (e.g.,when applied to a vertical surface); foam that dries to a clearappearance, e.g., that leaves no visible residue on a stainless steelsurface; and/or foam that can be applied with a moderate or low odorcompared to a conventional foam containing peroxyacetic acid.

Anionic sulfate surfactants suitable for use in the present compositionsinclude alkyl ether sulfates, alkyl sulfates, the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, theC₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl) glucaminesulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like. Also included are the alkyl sulfates,alkyl poly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy)sulfates such as the sulfates or condensation products of ethylene oxideand nonyl phenol (usually having 1 to 6 oxyethylene groups permolecule).

Anionic carboxylate surfactants suitable for use in the presentcompositions include carboxylic acids (and salts), such as alkanoicacids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates),ether carboxylic acids, and the like. Such carboxylates include alkylethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxypolycarboxylate surfactants and soaps (e.g. alkyl carboxyls). Secondarycarboxylates useful in the present compositions include those whichcontain a carboxyl unit connected to a secondary carbon. The secondarycarbon can be in a ring structure, e.g. as in p-octyl benzoic acid, oras in alkyl-substituted cyclohexyl carboxylates. The secondarycarboxylate surfactants typically contain no ether linkages, no esterlinkages and no hydroxyl groups. Further, they typically lack nitrogenatoms in the head-group (amphiphilic portion). Suitable secondary soapsurfactants typically contain 11-13 total carbon atoms, although morecarbons atoms (e.g., up to 16) can be present. Suitable carboxylatesalso include acylamino acids (and salts), such as acylgluamates, acylpeptides, sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyltaurates and fatty acid amides of methyl tauride), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of Formula 3:R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂X  (3)in which R is a C₈ to C₂₂ alkyl group or

in which R¹ is a C₄-C₁₆ alkyl group; n is an integer of 1-20; m is aninteger of 1-3; and X is a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In an embodiment, in Formula 3, n isan integer of 4 to 10 and m is 1. In an embodiment, in Formula 3, R is aC₈-C₁₆ alkyl group. In an embodiment, in Formula 3, R is a C₁₂-C₁₄ alkylgroup, n is 4, and m is 1.

In an embodiment, in Formula 3, R is

and R¹ is a C₆-C₁₂ alkyl group. In an embodiment, in Formula 3, R¹ is aC₉ alkyl group, n is 10 and m is 1. Such alkyl and alkylaryl ethoxycarboxylates are commercially available. These ethoxy carboxylates aretypically available as the acid forms, which can be readily converted tothe anionic or salt form. Commercially available carboxylates include,Neodox 23-4, a C₁₂₋₁₃ alkyl polyethoxy (4) carboxylic acid (ShellChemical), and Emcol CNP-110, a C₉ alkylaryl polyethoxy (10) carboxylicacid (Witco Chemical). Carboxylates are also available from Clariant,e.g. the product Sandopan® DTC, a C₁₃ alkyl polyethoxy (7) carboxylicacid.Amphoteric Surfactants

Amphoteric, or ampholytic, surfactants contain both a basic and anacidic hydrophilic group and an organic hydrophobic group. These ionicentities may be any of anionic or cationic groups described herein forother types of surfactants. A basic nitrogen and an acidic carboxylategroup are the typical functional groups employed as the basic and acidichydrophilic groups. In a few surfactants, sulfonate, sulfate,phosphonate or phosphate provide the negative charge.

Amphoteric surfactants can be broadly described as derivatives ofaliphatic secondary and tertiary amines, in which the aliphatic radicalmay be straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group, e.g., carboxy, sulfo, sulfato,phosphato, or phosphono. Amphoteric surfactants are subdivided into twomajor classes known to those of skill in the art and described in“Surfactant Encyclopedia” Cosmetics & Toiletries, Vol. 104 (2) 69-71(1989). The first class includes acyl/dialkyl ethylenediaminederivatives (e.g. 2-alkyl hydroxyethyl imidazoline derivatives) andtheir salts. The second class includes N-alkylamino acids and theirsalts. Some amphoteric surfactants can be envisioned as fitting intoboth classes.

Amphoteric surfactants can be synthesized by methods known to those ofskill in the art. For example, 2-alkyl hydroxyethyl imidazoline issynthesized by condensation and ring closure of a long chain carboxylicacid (or a derivative) with dialkyl ethylenediamine. Commercialamphoteric surfactants are derivatized by subsequent hydrolysis andring-opening of the imidazoline ring by alkylation—for example withchloroacetic acid or ethyl acetate. During alkylation, one or twocarboxy-alkyl groups react to form a tertiary amine and an ether linkagewith differing alkylating agents yielding different tertiary amines.

Long chain imidazoline derivatives having application in the presentinvention generally have the general formula:

wherein R is an acyclic hydrophobic group containing from about 8 to 18carbon atoms and M is a cation to neutralize the charge of the anion,generally sodium. Commercially prominent imidazoline-derived amphotericsthat can be employed in the present compositions include for example:Cocoamphopropionate, Cocoamphocarboxy-propionate, Cocoamphoglycinate,Cocoamphocarboxy-glycinate, Cocoamphopropyl-sulfonate, andCocoamphocarboxy-propionic acid. Amphocarboxylic acids can be producedfrom fatty imidazolines in which the dicarboxylic acid functionality ofthe amphodicarboxylic acid is diacetic acid and/or dipropionic acid.

The carboxymethylated compounds (glycinates) described herein abovefrequently are called betaines. Betaines are a special class ofamphoteric discussed herein below in the section entitled, ZwitterionSurfactants.

Long chain N-alkylamino acids are readily prepared by reaction RNH₂, inwhich R═C₈-C₁₈ straight or branched chain alkyl, fatty amines withhalogenated carboxylic acids. Alkylation of the primary amino groups ofan amino acid leads to secondary and tertiary amines. Alkyl substituentsmay have additional amino groups that provide more than one reactivenitrogen center. Most commercial N-alkylamine acids are alkylderivatives of beta-alanine or beta-N(2-carboxyethyl) alanine. Examplesof commercial N-alkylamino acid ampholytes having application in thisinvention include alkyl beta-amino dipropionates, RN(C₂H₄COOM)₂ andRNHC₂H₄COOM. In an embodiment, R can be an acyclic hydrophobic groupcontaining from about 8 to about 18 carbon atoms, and M is a cation toneutralize the charge of the anion.

Suitable amphoteric surfactants include those derived from coconutproducts such as coconut oil or coconut fatty acid. Additional suitablecoconut derived surfactants include as part of their structure anethylenediamine moiety, an alkanolamide moiety, an amino acid moiety,e.g., glycine, or a combination thereof; and an aliphatic substituent offrom about 8 to 18 (e.g., 12) carbon atoms. Such a surfactant can alsobe considered an alkyl amphodicarboxylic acid. These amphotericsurfactants can include chemical structures represented as:C₁₂-alkyl-C(O)—NH—CH₂—CH₂—N⁺(CH₂—CH₂—CO₂Na)₂—CH₂—CH₂—OH orC₁₂-alkyl-C(O)—N(H)—CH₂—CH₂—N⁺(CH₂—CO₂Na)₂—CH₂—CH₂—OH. Disodiumcocoampho dipropionate is one suitable amphoteric surfactant and iscommercially available under the tradename Miranol™ FBS from RhodiaInc., Cranbury, N.J. Another suitable coconut derived amphotericsurfactant with the chemical name disodium cocoampho diacetate is soldunder the tradename Mirataine™ JCHA, also from Rhodia Inc., Cranbury,N.J.

A typical listing of amphoteric classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).

Zwitterionic Surfactants

Zwitterionic surfactants can be thought of as a subset of the amphotericsurfactants and can include an anionic charge. Zwitterionic surfactantscan be broadly described as derivatives of secondary and tertiaryamines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Typically, a zwitterionic surfactant includes apositive charged quaternary ammonium or, in some cases, a sulfonium orphosphonium ion; a negative charged carboxyl group; and an alkyl group.Zwitterionics generally contain cationic and anionic groups which ionizeto a nearly equal degree in the isoelectric region of the molecule andwhich can develop strong “inner-salt” attraction betweenpositive-negative charge centers. Examples of such zwitterionicsynthetic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight chain or branched, and wherein one of thealiphatic substituents contains from 8 to 18 carbon atoms and onecontains an anionic water solubilizing group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate. Betaine and sultaine surfactants areexemplary zwitterionic surfactants for use herein.

A general formula for these compounds is:

wherein R¹ contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from0 to 1 glyceryl moiety; Y is selected from the group consisting ofnitrogen, phosphorus, and sulfur atoms; R² is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfuratom and 2 when Y is a nitrogen or phosphorus atom, R³ is an alkylene orhydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Zis a radical selected from the group consisting of carboxylate,sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of zwitterionic surfactants having the structures listed aboveinclude:4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate;5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate;3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate;3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate;3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulfonate;4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate;3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate;3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; andS[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate.The alkyl groups contained in said detergent surfactants can be straightor branched and saturated or unsaturated.

The zwitterionic surfactant suitable for use in the present compositionsincludes a betaine of the general structure:

These surfactant betaines typically do not exhibit strong cationic oranionic characters at pH extremes nor do they show reduced watersolubility in their isoelectric range. Unlike “external” quaternaryammonium salts, betaines are compatible with anionics. Examples ofsuitable betaines include coconut acylamidopropyldimethyl betaine;hexadecyl dimethyl betaine; C₁₂₋₁₄ acylamidopropylbetaine; C₈₋₁₄acylamidohexyldiethyl betaine; 4-C₁₄₋₁₆acylmethylamidodiethylammonio-1-carboxybutane; C₁₆₋₁₈acylamidodimethylbetaine; C₁₂₋₁₆ acylamidopentanediethylbetaine; andC₁₂₋₁₆ acylmethylamidodimethylbetaine.

Sultaines useful in the present invention include those compounds havingthe formula R(R¹)₂ N⁺R²SO³⁻, in which R is a C₆-C₁₈ hydrocarbyl group,each R¹ is typically independently C₁-C₃ alkyl, e.g. methyl, and R² is aC₁-C₆ hydrocarbyl group, e.g. a C₁-C₃ alkylene or hydroxyalkylene group.

A typical listing of zwitterionic classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).

In an embodiment, the composition of the present invention includes abetaine. For example, the composition can include cocoamidopropylbetaine.

Embodiments of Compositions

Some examples of representative constituent concentrations forembodiments of the present compositions can be found in Tables A-C, inwhich the values are given in wt-% of the ingredients in reference tothe total composition weight. In certain embodiments, the proportionsand amounts in Tables A-C can be modified by “about”.

TABLE A Ingredient wt-% wt-% wt-% wt-% medium chain 0.3-7   0.5-5  0.5-4   1-3 peroxycarboxylic acid medium chain 1-10 2-8  2-6 2.5-5  carboxylic acid solubilizer 1-80 2-70  3-65  5-60 carrier 0-98 5-9010-80 20-70

TABLE B Ingredient wt-% wt-% wt-% wt-% medium chain 0.3-7   0.5-5  0.5-4   1-3 peroxycarboxylic acid medium chain 1-10 2-8 3-6 3-5carboxylic acid solubilizer 1-80  5-70 10-65 20-60 carrier 0-98 0.2-60 5-20 20-40

TABLE C Ingredient wt-% wt-% wt-% wt-% medium chain 0.3-7   0.5-5  0.5-4 1-2 peroxycarboxylic acid medium chain 1-10 1-8 1.5-6 2-4carboxylic acid solubilizer 1-25  2-20   3-15  4-10 carrier 5-97 10-90  15-70 30-75

Some examples of representative constituent concentrations foradditional embodiments of the present compositions can be found inTables D-F, in which the values are given in wt-% of the ingredients inreference to the total composition weight. In certain embodiments, theproportions and amounts in Tables D-F can be modified by “about”.

TABLE D Ingredient wt-% wt-% wt-% wt-% medium chain 0.3-7   0.5-5  0.5-4   1-3 peroxycarboxylic acid medium chain 1-10 2-8  2-6 2.5-5  carboxylic acid solubilizer 1-80 2-70  3-65  5-60 carrier 0-98 5-9010-80 20-70 oxidizing agent 2-30 2-25  4-20  6-10 acidulant 1-50 2-40 3-40  5-40 stabilizing agent 1-50 1-10 1-5 1-3

TABLE E Ingredient wt-% wt-% wt-% wt-% medium chain 0.3-7   0.5-5  0.5-4   1-3 peroxycarboxylic acid medium chain 1-10 2-8  3-6 3-5carboxylic acid solubilizer 1-80 5-70 10-65 20-60 carrier 0-98 0.2-60   5-20 20-40 oxidizing agent 2-30 2-25  4-20  6-10 acidulant 1-50 2-40 3-40  5-40 stabilizing agent 1-50 1-10 1-5 1-3

TABLE F Ingredient wt-% wt-% wt-% wt-% medium chain 0.3-7   0.5-5  0.5-4   1-2 peroxycarboxylic acid medium chain 1-10 1-8  1.5-6   2-4carboxylic acid solubilizer 1-25 2-20 3-15  4-10 carrier 5-97 10-90 15-70  30-75 oxidizing agent 2-30 2-25 4-20  6-10 acidulant 1-50 2-403-35  5-30 stabilizing agent 1-50 1-15 1-5  1-3

In an embodiment, the compositions of the present invention include onlyingredients that can be employed in food products or in food wash,handling, or processing, for example, according to government (e.g. FDAor USDA) rules and regulations, 21 CFR §170-178. In an embodiment, thecompositions of the present invention can include only ingredients atthe concentrations approved for incidental food contact by the USEPA, 40CFR §180.940.

The present compositions can take the form of a liquid, solid, gel,paste, unit dose, gel pack, or the like. The present compositions can besupplied in any of a variety of containers or media, such as in a 2compartment dispenser or as a pre-moistened wipe, towelette, or sponge.

Carrier

The composition of the invention can also include a carrier. The carrierprovides a medium which dissolves, suspends, or carries the othercomponents of the composition. For example, the carrier can provide amedium for solubilization, suspension, or production of peroxycarboxylicacid and for forming an equilibrium mixture. The carrier can alsofunction to deliver and wet the antimicrobial composition of theinvention on an object. To this end, the carrier can contain anycomponent or components that can facilitate these functions.

In certain embodiments, the carrier includes primarily water which canpromote solubility and work as a medium for reaction and equilibrium.The carrier can include or be primarily an organic solvent, such assimple alkyl alcohols, e.g., ethanol, isopropanol, n-propanol, and thelike. Polyols are also useful carriers, including glycerol, sorbitol,and the like.

Suitable carriers include glycol ethers. Suitable glycol ethers includediethylene glycol n-butyl ether, diethylene glycol n-propyl ether,diethylene glycol ethyl ether, diethylene glycol methyl ether,diethylene glycol t-butyl ether, dipropylene glycol n-butyl ether,dipropylene glycol methyl ether, dipropylene glycol ethyl ether,dipropylene glycol propyl ether, dipropylene glycol tert-butyl ether,ethylene glycol butyl ether, ethylene glycol propyl ether, ethyleneglycol ethyl ether, ethylene glycol methyl ether, ethylene glycol methylether acetate, propylene glycol n-butyl ether, propylene glycol ethylether, propylene glycol methyl ether, propylene glycol n-propyl ether,tripropylene glycol methyl ether and tripropylene glycol n-butyl ether,ethylene glycol phenyl ether (commercially available as DOWANOL EPH™from Dow Chemical Co.), propylene glycol phenyl ether (commerciallyavailable as DOWANOL PPH™ from Dow Chemical Co.), and the like, ormixtures thereof. Additional suitable commercially available glycolethers (all of which are available from Union Carbide Corp.) includeButoxyethyl PROPASOL™, Butyl CARBITOL™ acetate, Butyl CARBITOL™, ButylCELLOSOLVE™ acetate, Butyl CELLOSOLVE™, Butyl DIPROPASOL™, ButylPROPASOL™, CARBITOL™ PM-600, CARBITOL™ Low Gravity, CELLOSOLVE™ acetate,CELLOSOLVE™, Ester EEP™, FILMER IBT™, Hexyl CARBITOL™, HexylCELLOSOLVE™, Methyl CARBITOL™, Methyl CELLOSOLVE™ acetate, MethylCELLOSOLVE™, Methyl DIPROPASOL™, Methyl PROPASOL™ acetate, MethylPROPASOL™, Propyl CARBITOL™, Propyl CELLOSOLVE™, Propyl DIPROPASOL™ andPropyl PROPASOL™.

In certain embodiments, the carrier makes up a large portion of thecomposition of the invention and may be the balance of the compositionapart from the active antimicrobial components, solubilizer, oxidizingagent, adjuvants, and the like. Here again, the carrier concentrationand type will depend upon the nature of the composition as a whole, theenvironmental storage, and method of application including concentrationof the medium chain peroxycarboxylic acid, among other factors. Notablythe carrier should be chosen and used at a concentration which does notinhibit the antimicrobial efficacy of the medium chain peroxycarboxylicacid in the composition of the invention.

In certain embodiments, the present composition includes about 0 toabout 98 wt-% carrier, about 0.001 to about 99.99 wt-% carrier, about0.2 to about 60 wt-% carrier, about 1 to about 98 wt-% carrier, about 5to about 99.99 wt-% carrier, about 5 to about 97 wt-% carrier, about 5to about 90 wt-% carrier, about 5 to about 70 wt-% carrier, about 5 toabout 20 wt-% carrier, about 10 to about 90 wt-% carrier, about 10 toabout 80 wt-% carrier, about 10 to about 50 wt-% carrier, about 10 toabout 20 wt-% carrier, about 15 to about 70 wt-% carrier, about 15 toabout 80 wt-% carrier, about 20 to about 70 wt-% carrier, about 20 toabout 50 wt-% carrier, about 20 to about 40 wt-% carrier, about 20 toabout 30 wt-% carrier, about 30 to about 75 wt-% carrier, about 30 toabout 70 wt-% carrier, about 40 to about 99.99 wt-% carrier, about 40 toabout 90 wt-% carrier, or about 60 to about 70 wt-% carrier. Thecomposition can include any of these ranges or amounts not modified byabout.

Oxidizing Agent

The present compositions and methods can include any of a variety ofoxidizing agents. The oxidizing agent can be used for maintaining orgenerating peroxycarboxylic acids.

Examples of inorganic oxidizing agents include the following types ofcompounds or sources of these compounds, or alkali metal salts includingthese types of compounds, or forming an adduct therewith:

-   -   hydrogen peroxide;    -   group 1 (IA) oxidizing agents, for example lithium peroxide,        sodium peroxide, and the like;    -   group 2 (IIA) oxidizing agents, for example magnesium peroxide,        calcium peroxide, strontium peroxide, barium peroxide, and the        like;    -   group 12 (IIB) oxidizing agents, for example zinc peroxide, and        the like;    -   group 13 (IIIA) oxidizing agents, for example boron compounds,        such as perborates, for example sodium perborate hexahydrate of        the formula Na₂[Br₂(O₂)₂(OH)₄].6H₂O (also called sodium        perborate tetrahydrate and formerly written as NaBO₃.4H₂O);        sodium peroxyborate tetrahydrate of the formula        Na₂Br₂(O₂)₂[(OH)₄].4H₂O (also called sodium perborate        trihydrate, and formerly written as NaBO₃.3H₂O); sodium        peroxyborate of the formula Na₂[B₂(O₂)₂(OH)₄] (also called        sodium perborate monohydrate and formerly written as NaBO₃.H₂O);        and the like; in an embodiment, perborate;    -   group 14 (IVA) oxidizing agents, for example persilicates and        peroxycarbonates, which are also called percarbonates, such as        persilicates or peroxycarbonates of alkali metals; and the like;        in an embodiment, percarbonate; in an embodiment, persilicate;    -   group 15 (VA) oxidizing agents, for example peroxynitrous acid        and its salts; peroxyphosphoric acids and their salts, for        example, perphosphates; and the like; in an embodiment,        perphosphate;    -   group 16 (VIA) oxidizing agents, for example peroxysulfuric        acids and their salts, such as peroxymonosulfuric and        peroxydisulfuric acids, and their salts, such as persulfates,        for example, sodium persulfate; and the like; in an embodiment,        persulfate;    -   group VIIa oxidizing agents such as sodium periodate, potassium        perchlorate and the like.

Other active inorganic oxygen compounds can include transition metalperoxides; and other such peroxygen compounds, and mixtures thereof.

In an embodiment, the compositions and methods of the present inventionemploy one or more (e.g., at least one) of the inorganic oxidizingagents listed above. Suitable inorganic oxidizing agents include ozone,hydrogen peroxide, hydrogen peroxide adduct, group IIIA oxidizing agent,group VIA oxidizing agent, group VA oxidizing agent, group VIIAoxidizing agent, or mixtures thereof. Suitable examples of suchinorganic oxidizing agents include percarbonate, perborate, persulfate,perphosphate, persilicate, or mixtures thereof.

Hydrogen peroxide presents one suitable example of an inorganicoxidizing agent. Hydrogen peroxide can be provided as a mixture ofhydrogen peroxide and water, e.g., as liquid hydrogen peroxide in anaqueous solution. Hydrogen peroxide is commercially available atconcentrations of 35%, 70%, and 90% in water. For safety, the 35% iscommonly used. The present compositions can include, for example, about2 to about 30 wt-% or about 5 to about 20 wt-% hydrogen peroxide.

In an embodiment, the inorganic oxidizing agent includes hydrogenperoxide adduct. For example, the inorganic oxidizing agent can includehydrogen peroxide, hydrogen peroxide adduct, or mixtures thereof. Any ofa variety of hydrogen peroxide adducts are suitable for use in thepresent compositions and methods. For example, suitable hydrogenperoxide adducts include percarbonate salt, urea peroxide, peracetylborate, an adduct of H₂O₂ and polyvinyl pyrrolidone, sodiumpercarbonate, potassium percarbonate, mixtures thereof, or the like.Suitable hydrogen peroxide adducts include percarbonate salt, ureaperoxide, peracetyl borate, an adduct of H₂O₂ and polyvinyl pyrrolidone,or mixtures thereof. Suitable hydrogen peroxide adducts include sodiumpercarbonate, potassium percarbonate, or mixtures thereof, for examplesodium percarbonate.

In an embodiment, the present compositions and methods can includehydrogen peroxide as oxidizing agent. Hydrogen peroxide in combinationwith the percarboxylic acid can provide certain antimicrobial actionagainst microorganisms. Additionally, hydrogen peroxide can provide aneffervescent action which can irrigate any surface to which it isapplied. Hydrogen peroxide can work with a mechanical flushing actiononce applied which further cleans the surface of an object. Anadditional advantage of hydrogen peroxide is the food compatibility ofthis composition upon use and decomposition.

In certain embodiments, the present composition includes about 0.001 toabout 30 wt-% oxidizing agent, about 0.001 to about 10 wt-% oxidizingagent, 0.002 to about 10 wt-% oxidizing agent, about 2 to about 30 wt-%oxidizing agent, about 2 to about 25 wt-% oxidizing agent, about 2 toabout 20 wt-% oxidizing agent, about 4 to about 20 wt-% oxidizing agent,about 5 to about 10 wt-% oxidizing agent, or about 6 to about 10 wt-%oxidizing agent. The composition can include any of these ranges oramounts not modified by about.

Acidulant

In an embodiment, the present composition can include an acidulant. Theacidulant can act as a catalyst for conversion of carboxylic acid toperoxycarboxylic acid. The acidulant can be effective to form aconcentrate composition with pH of about 1 or less. The acidulant can beeffective to form a use composition with pH of about 5, about 5 or less,about 4, about 4 or less, about 3, about 3 or less, about 2, about 2 orless, or the like. In an embodiment, the acidulant includes an inorganicacid. Suitable inorganic acids include sulfuric acid, phosphoric acid,nitric acid, hydrochloric acid, methane sulfonic acid, ethane sulfonicacid, propane sulfonic acid, butane sulfonic acid, xylene sulfonic acid,benzene sulfonic acid, mixtures thereof, or the like.

In an embodiment, the acidulant includes a carboxylic acid with pK_(a)less than 4. Suitable carboxylic acids with pK_(a) less than 4 includehydroxyacetic acid, hydroxypropionic acid, other hydroxycarboxylicacids, mixtures thereof, or the like. Such an acidulant is present at aconcentration where it does not act as a solubilizer.

In certain embodiments, the present composition includes about 0.001 toabout 50 wt-% acidulant, about 0.001 to about 30 wt-% acidulant, about 1to about 50 wt-% acidulant, about 1 to about 30 wt-% acidulant, about 2to about 40 wt-% acidulant, about 2 to about 10 wt-% acidulant, about 3to about 40 wt-% acidulant, about 5 to about 40 wt-% acidulant, about 5to about 25 wt-% acidulant, about 10 to about 40 wt-% acidulant, about10 to about 30 wt-% acidulant, about 15 to about 35 wt-% acidulant,about 15 to about 30 wt-% acidulant, or about 40 to about 60 wt-%acidulant. The composition can include any of these ranges or amountsnot modified by about.

Stabilizing Agent

One or more stabilizing agents can be added to the composition of theinvention, for example, to stabilize the peracid and hydrogen peroxideand prevent the premature oxidation of this constituent within thecomposition of the invention.

Suitable stabilizing agents include chelating agents or sequestrants.Suitable sequestrants include organic chelating compounds that sequestermetal ions in solution, particularly transition metal ions. Suchsequestrants include organic amino- or hydroxy-polyphosphonic acidcomplexing agents (either in acid or soluble salt forms), carboxylicacids (e.g., polymeric polycarboxylate), hydroxycarboxylic acids, oraminocarboxylic acids.

The sequestrant can be or include phosphonic acid or phosphonate salt.Suitable phosphonic acids and phosphonate salts include 1-hydroxyethylidene-1,1-diphosphonic acid (CH₃C(PO₃H₂)₂OH) (HEDP);ethylenediamine tetrakis methylenephosphonic acid (EDTMP);diethylenetriamine pentakis methylenephosphonic acid (DTPMP);cyclohexane-1,2-tetramethylene phosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylene diamine[tetra methylene-phosphonic acid)];2-phosphene butane-1,2,4-tricarboxylic acid; or salts thereof, such asthe alkali metal salts, ammonium salts, or alkyloyl amine salts, such asmono, di, or tetra-ethanolamine salts; or mixtures thereof.

Suitable organic phosphonates include HEDP.

Commercially available food additive chelating agents includephosphonates sold under the trade name DEQUEST® including, for example,1-hydroxyethylidene-1,1-diphosphonic acid, available from MonsantoIndustrial Chemicals Co., St. Louis, Mo., as DEQUEST® 2010;amino(tri(methylenephosphonic acid)), (N[CH₂PO₃H₂]₃), available fromMonsanto as DEQUEST® 2000; ethylenediamine[tetra(methylenephosphonicacid)] available from Monsanto as DEQUEST® 2041; and2-phosphonobutane-1,2,4-tricarboxylic acid available from Mobay ChemicalCorporation, Inorganic Chemicals Division, Pittsburgh, Pa., as BayhibitAM.

The sequestrant can be or include aminocarboxylic acid type sequestrant.Suitable aminocarboxylic acid type sequestrants include the acids oralkali metal salts thereof, e.g., amino acetates and salts thereof.Suitable aminocarboxylates include N-hydroxyethylaminodiacetic acid;hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA);ethylenediaminetetraacetic acid (EDTA);N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA);diethylenetriaminepentaacetic acid (DTPA); and alanine-N,N-diaceticacid; and the like; and mixtures thereof.

The sequestrant can be or include a polycarboxylate. Suitablepolycarboxylates include, for example, polyacrylic acid, maleic/olefincopolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylicacid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzedpolymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers,hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile,hydrolyzed acrylonitrile-methacrylonitrile copolymers, polymaleic acid,polyfumaric acid, copolymers of acrylic and itaconic acid, phosphinopolycarboxylate, acid or salt forms thereof, mixtures thereof, and thelike.

In certain embodiments, the present composition includes about 0.5 toabout 50 wt-% sequestrant, about 1 to about 50 wt-% sequestrant, about 1to about 30 wt-% sequestrant, about 1 to about 15 wt-% sequestrant,about 1 to about 5 wt-% sequestrant, about 1 to about 4 wt-%sequestrant, about 2 to about 10 wt-% sequestrant, about 2 to about 5wt-% sequestrant, or about 5 to about 15 wt-% sequestrant. Thecomposition can include any of these ranges or amounts not modified byabout.

In certain embodiments, the present composition includes about 0.001 toabout 50 wt-% stabilizing agent, about 0.001 to about 5 wt-% stabilizingagent, about 0.5 to about 50 wt-% stabilizing agent, about 1 to about 50wt-% stabilizing agent, about 1 to about 30 wt-% stabilizing agent,about 1 to about 10 wt-% stabilizing agent, about 1 to about 5 wt-%stabilizing agent, about 1 to about 3 wt-% stabilizing agent, about 2 toabout 10 wt-% stabilizing agent, about 2 to about 5 wt-% stabilizingagent, or about 5 to about 15 wt-% stabilizing agent. The compositioncan include any of these ranges or amounts not modified by about.

Adjuvants

The antimicrobial composition of the invention can also include anynumber of adjuvants. Specifically, the composition of the invention caninclude antimicrobial solvent, antimicrobial agent, wetting agent,defoaming agent, thickener, a surfactant, foaming agent, solidificationagent, aesthetic enhancing agent (i.e., colorant (e.g., pigment),odorant, or perfume), among any number of constituents which can beadded to the composition. Such adjuvants can be preformulated with theantimicrobial composition of the invention or added to the systemsimultaneously, or even after, the addition of the antimicrobialcomposition. The composition of the invention can also contain anynumber of other constituents as necessitated by the application, whichare known and which can facilitate the activity of the presentinvention.

Antimicrobial Solvent

Any of a variety of solvents can be useful as antimicrobial solvents inthe present compositions. Antimicrobial solvent can be added to usecompositions before use. Suitable antimicrobial solvents includeacetamidophenol; acetanilide; acetophenone; 2-acetyl-1-methylpyrrole;benzyl acetate; benzyl alcohol; benzyl benzoate; benzyloxyethanol;essential oils (e.g., benzaldehyde, pinenes, terpineols, terpinenes,carvone, cinnamealdehyde, bomeol and its esters, citrals, ionenes,jasmine oil, limonene, dipentene, linalool and its esters); diesterdicarboxylates (e.g., dibasic esters) such as dimethyl adipate, dimethylsuccinate, dimethyl glutarate (including products available under thetrade designations DBE, DBE-3, DBE-4, DBE-5, DBE-6, DBE-9, DBE-IB, andDBE-ME from DuPont Nylon), dimethyl malonate, diethyl adipate, diethylsuccinate, diethyl glutarate, dibutyl succinate, and dibutyl glutarate;dimethyl sebacate, dimethyl pimelate, dimethyl suberate; dialkylcarbonates such as dimethyl carbonate, diethyl carbonate, dipropylcarbonate, diisopropyl carbonate, and dibutyl carbonate; organo-nitrilessuch as acetonitrile and benzonitrile; and phthalate esters such asdibutyl phthalate, diethylhexyl phthalate, and diethyl phthalate.Mixtures of antimicrobial solvents can be used if desired.

The antimicrobial solvent can be selected based upon the characteristicsof the surface and microbes to which the antimicrobial composition willbe applied and upon the nature of any coating, soil or other materialthat will be contacted by the antimicrobial composition and optionallyremoved from the surface. Polar solvents, and solvents that are capableof hydrogen bonding typically will perform well on a variety of surfacesand microbes and thus, for such applications, can be selected. Incertain applications, the antimicrobial solvent can be selected for ahigh flashpoint (e.g., greater than about 30° C., greater than about 50°C., or greater than about 100° C.), low odor, and low human and animaltoxicity.

In an embodiment, the antimicrobial solvent is compatible as an indirector direct food additive or substance; especially those described in theCode of Federal Regulations (CFR), Title 21—Food and Drugs, parts 170 to186. The compositions of the invention should contain sufficientantimicrobial solvent to provide the desired rate and type of microbialreduction.

The present composition can include an effective amount of antimicrobialsolvent, such as about 0.01 wt-% to about 60 wt-% antimicrobial solvent,about 0.05 wt-% to about 15 wt-% antimicrobial solvent, or about 0.08wt-% to about 5 wt-% antimicrobial solvent.

Additional Antimicrobial Agent

The antimicrobial compositions of the invention can contain anadditional antimicrobial agent. Additional antimicrobial agent can beadded to use compositions before use. Suitable antimicrobial agentsinclude carboxylic esters (e.g., p-hydroxy alkyl benzoates and alkylcinnamates), sulfonic acids (e.g., dodecylbenzene sulfonic acid),iodo-compounds or active halogen compounds (e.g., elemental halogens,halogen oxides (e.g., NaOCl, HOCl, HOBr, ClO₂), iodine, interhalides(e.g., iodine monochloride, iodine dichloride, iodine trichloride,iodine tetrachloride, bromine chloride, iodine monobromide, or iodinedibromide), polyhalides, hypochlorite salts, hypochlorous acid,hypobromite salts, hypobromous acid, chloro- and bromo-hydantoins,chlorine dioxide, and sodium chlorite), organic peroxides includingbenzoyl peroxide, alkyl benzoyl peroxides, ozone, singlet oxygengenerators, and mixtures thereof, phenolic derivatives (e.g., o-phenylphenol, o-benzyl-p-chlorophenol, tert-amyl phenol and C₁-C₆ alkylhydroxy benzoates), quaternary ammonium compounds (e.g.,alkyldimethylbenzyl ammonium chloride, dialkyldimethyl ammonium chlorideand mixtures thereof), and mixtures of such antimicrobial agents, in anamount sufficient to provide the desired degree of microbial protection.

The present composition can include an effective amount of antimicrobialagent, such as about 0.001 wt-% to about 60 wt-% antimicrobial agent,about 0.01 wt-% to about 15 wt-% antimicrobial agent, or about 0.08 wt-%to about 2.5 wt-% antimicrobial agent.

Wetting or Defoaming Agents

Also useful in the composition of the invention are wetting anddefoaming agents. Wetting agents function to increase the surfacecontact or penetration activity of the antimicrobial composition of theinvention. Wetting agents which can be used in the composition of theinvention include any of those constituents known within the art toraise the surface activity of the composition of the invention.

Suitable defoamers which can be used in accordance with the inventioninclude silica and silicones; aliphatic acids or esters; alcohols;sulfates or sulfonates; amines or amides; halogenated compounds such asfluorochlorohydrocarbons; vegetable oils, waxes, mineral oils as well astheir sulfated derivatives; fatty acid soaps such as alkali, alkalineearth metal soaps; and phosphates and phosphate esters such as alkyl andalkaline diphosphates, and tributyl phosphates among others; andmixtures thereof.

In an embodiment, the present compositions can include antifoamingagents or defoamers which are of food grade quality given theapplication of the method of the invention. To this end, one of the moreeffective antifoaming agents includes silicones. Silicones such asdimethyl silicone, glycol polysiloxane, methylphenol polysiloxane,trialkyl or tetralkyl silanes, hydrophobic silica defoamers and mixturesthereof can all be used in defoaming applications. Commercial defoamerscommonly available include silicones such as Ardefoam® from ArmourIndustrial Chemical Company which is a silicone bound in an organicemulsion; Foam Kill® or Kresseo® available from Krusable ChemicalCompany which are silicone and non-silicone type defoamers as well assilicone esters; and Anti-Foam A® and DC-200 from Dow CorningCorporation which are both food grade type silicones among others. Thesedefoamers can be present at a concentration range from about 0.01 wt-%to 5 wt-%, from about 0.01 wt-% to 2 wt-%, or from about 0.01 wt-% toabout 1 wt-%.

Thickening or Gelling Agents

The present compositions can include any of a variety of knownthickeners. Suitable thickeners include natural gums such as xanthangum, guar gum, or other gums from plant mucilage; polysaccharide basedthickeners, such as alginates, starches, and cellulosic polymers (e.g.,carboxymethyl cellulose); polyacrylates thickeners; and hydrocolloidthickeners, such as pectin. In an embodiment, the thickener does notleave contaminating residue on the surface of an object. For example,the thickeners or gelling agents can be compatible with food or othersensitive products in contact areas. Generally, the concentration ofthickener employed in the present compositions or methods will bedictated by the desired viscosity within the final composition. However,as a general guideline, the viscosity of thickener within the presentcomposition ranges from about 0.1 wt-% to about 1.5 wt-%, from about 0.1wt-% to about 1.0 wt-%, or from about 0.1 wt-% to about 0.5 wt-%.

Solidification Agent

The present compositions can include a solidification agent, which canparticipate in maintaining the compositions in a solid form. Suitablesolidification agents include a solid polyethylene glycol (PEG), a solidEO/PO block copolymer, and the like; an amide, such as stearicmonoethanolamide, lauric diethanolamide, an alkylamide, or the like;starches that have been made water-soluble through an acid or alkalinetreatment process; celluloses that have been made water-soluble; aninorganic agent, or the like; poly(maleic anhydride/methyl vinyl ether);polymethacrylic acid; other generally functional or inert materials withhigh melting points; and the like.

In certain embodiments, the solidification agent includes solid PEG, forexample PEG 1500 up to PEG 20,000. In certain embodiments, the PEGincludes PEG 1450, PEG 3350, PEG 4500, PEG 8000, PEG 20,000, and thelike. Additional suitable solidification agents include EO/PO blockcopolymers such as those sold under the tradenames Pluronic 108,Pluronic F68; amides such as lauric diethanolamide or cocodiethyleneamide; and the like. In certain embodiments, the solidification agentincludes a combination of solidification agents, such as combination ofPEG and an EO/PO block copolymer (such as a Pluronic) and combination ofPEG and an amide (such as lauric diethanolamide amide or stearicmonoethanol amide).

Fragrance

In an embodiment, the present composition includes a fragrance. Thefragrance can be selected to avoid undesirable effects on the stabilityor efficacy of the composition. Suitable fragrances include amylacetate, iso-bomyl acetate, and alkyl salicylates, such as methylsalicylate. In an embodiment, the fragrance can include analkylsalicylate.

Additional Embodiments of the Medium Chain Peroxycarboxylic AcidCompositions

The present invention relates to compositions including medium chainperoxycarboxylic acid, methods for making these compositions, andmethods for reducing the population of a microorganism. In certainembodiments, the compositions can include advantageously high levels ofthe medium chain peroxycarboxylic acid, can be readily made, and/or canexhibit reduced odor.

In an embodiment, the present compositions can include medium chainperoxycarboxylic acid, medium chain carboxylic acid, carrier, andsolubilizer. In certain embodiments, the present compositions includeabout 2 or more parts of medium chain peroxycarboxylic acid for each 7parts of medium chain carboxylic acid; about 2 or more parts of mediumchain peroxycarboxylic acid for each 5 parts of medium chain carboxylicacid; about 2 or more parts of medium chain peroxycarboxylic acid foreach 4 parts of medium chain carboxylic acid; or about 2 parts of mediumchain peroxycarboxylic acid for each 3 parts of medium chain carboxylicacid.

In an embodiment, the solubilizer includes solvent, surfactant, ormixture thereof. In an embodiment, the surfactant solubilizer includes amicroemulsion forming surfactant, e.g., an anionic surfactant. In anembodiment, the composition includes a microemulsion. In an embodiment,the solubilizer includes polyalkylene oxide, capped polyalkylene oxide,nonionic surfactant, anionic surfactant, or mixture thereof. In anembodiment, the solvent solubilizer includes polyalkylene oxide, cappedpolyalkylene oxide, nonionic surfactant, or mixture thereof.

In an embodiment, the present compositions include no, onlyinsignificant, or relatively small amounts of short chainperoxycarboxylic acid, short chain carboxylic acid, or mixture thereof.For example, in an embodiment, the composition can be substantially freeof added short chain carboxylic acid, short chain peroxycarboxylic acid,or mixture thereof. For example, in an embodiment, the composition caninclude short chain carboxylic acid, short chain peroxycarboxylic acid,or mixture thereof at a level insufficient to solubilize medium chainperoxycarboxylic acid. For example, in an embodiment, the compositioncan include short chain carboxylic acid, short chain peroxycarboxylicacid, or mixture thereof at a level insufficient to cause objectionableodor. For example, in an embodiment, the composition can include about 1or more parts of medium chain peroxycarboxylic acid for each 8 parts ofshort chain carboxylic acid, short chain peroxycarboxylic acid, ormixture thereof.

In an embodiment, the composition also includes oxidizing agent,inorganic acid, stabilizing agent, another adjuvant or additive, ormixture thereof.

In an embodiment, the present invention includes a method of making amedium chain peroxycarboxylic acid composition. The method can includereacting medium chain carboxylic acid and oxidizing agent in thepresence of carrier, solubilizer, acidulant, stabilizing agent, ormixture thereof. The method can form advantageously high levels ofmedium chain peroxycarboxylic acids in advantageously short times. Forexample, in an embodiment, the present method includes converting 20% ormore of the medium chain carboxylic acid to medium chainperoxycarboxylic acid in about 24 or fewer hours. For example, in anembodiment, the present method includes converting about 25% or more ofthe medium chain carboxylic acid to medium chain peroxycarboxylic acidin about 24 or fewer hours. For example, in an embodiment, the presentmethod includes converting about 30% or more of the medium chaincarboxylic acid to medium chain peroxycarboxylic acid in about 24 orfewer hours. For example, in an embodiment, the present method includesconverting about 35% or more of the medium chain carboxylic acid tomedium chain peroxycarboxylic acid in about 24 or fewer hours. Forexample, in an embodiment, the present method includes converting about40% of the medium chain carboxylic acid to medium chain peroxycarboxylicacid in about 24 or fewer hours.

In an embodiment, the present invention includes a method of using amedium chain peroxycarboxylic acid composition. The method can includecontacting an object with the present composition (e.g., a usecomposition) and can result in reducing the population of one or moremicroorganisms on the object.

Use Compositions

The present compositions include concentrate compositions and usecompositions. For example, a concentrate composition can be diluted, forexample with water, to form a use composition. In an embodiment, aconcentrate composition can be diluted to a use solution before toapplication to an object. For reasons of economics, the concentrate canbe marketed and an end user can dilute the concentrate with water or anaqueous diluent to a use solution.

The level of active components in the concentrate composition isdependent on the intended dilution factor and the desired activity ofthe medium chain peroxycarboxylic acid compound. Generally, a dilutionof about 1 fluid ounce to about 20 gallons of water to about 5 fluidounces to about 1 gallon of water is used for aqueous antimicrobialcompositions. Higher use dilutions can be employed if elevated usetemperature (greater than 25° C.) or extended exposure time (greaterthan 30 seconds) can be employed. In the typical use locus, theconcentrate is diluted with a major proportion of water using commonlyavailable tap or service water mixing the materials at a dilution ratioof about 3 to about 20 ounces of concentrate per 100 gallons of water.

For example, a use composition can include about 0.01 to about 4 wt-% ofa concentrate composition and about 96 to about 99.99 wt-% diluent;about 0.5 to about 4 wt-% of a concentrate composition and about 96 toabout 99.5 wt-% diluent; about 0.5, about 1, about 1.5, about 2, about2.5, about 3, about 3.5, or about 4 wt-% of a concentrate composition;about 0.01 to about 0.1 wt-% of a concentrate composition; or about0.01, about 0.02, about 0.03, about 0.04, about 0.05, about 0.06, about0.07, about 0.08, about 0.09, or about 0.1 wt-% of a concentratecomposition. Amounts of an ingredient in a use composition can becalculated from the amounts listed above for concentrate compositionsand these dilution factors.

The present methods can employ medium chain peroxycarboxylic acid at aconcentration effective for reducing the population of one or moremicroorganisms. Such effective concentrations include about 2 to about500 ppm medium chain peroxycarboxylic acid, about 2 to about 300 ppmmedium chain peroxycarboxylic acid, about 5 to about 100 ppm mediumchain peroxycarboxylic acid, about 5 to about 60 ppm medium chainperoxycarboxylic acid, about 5 to about 45 ppm medium chainperoxycarboxylic acid, about 5 to about 35 ppm medium chainperoxycarboxylic acid, about 5 to about 25 ppm medium chainperoxycarboxylic acid, about 8 to about 50 ppm medium chainperoxycarboxylic acid, about 10 to about 500 ppm medium chainperoxycarboxylic acid, about 10 to about 50 ppm medium chainperoxycarboxylic acid, about 40 to about 140 ppm medium chainperoxycarboxylic acid, about 100 to about 250 ppm medium chainperoxycarboxylic acid, or about 200 to about 300 ppm medium chainperoxycarboxylic acid. In an embodiment, the use composition can includeabout 2 to about 500 ppm medium chain peroxycarboxylic acid, about 5 toabout 2000 ppm medium chain carboxylic acid, about 95 to about 99.99wt-% carrier and/or diluent (e.g., water); and about 2 to about 23,000ppm polyalkylene oxide, capped polyalkylene oxide, alkoxylatedsurfactant, anionic surfactant, or mixture thereof.

The level of reactive species, such as peroxycarboxylic acids and/orhydrogen peroxide, in a use composition can be affected, typicallydiminished, by organic matter that is found in or added to the usecomposition. For example, when the use composition is a bath or sprayused for washing an object, soil on the object can consume peroxy acidand peroxide. Thus, the present amounts of ingredients in the usecompositions refer to the composition before or early in use, with theunderstanding that the amounts will diminish as organic matter is addedto the use composition.

In an embodiment, the present use composition can be made more acidic bypassing the concentrate through an acidifying column, or by addingadditional acidulant to the use composition.

Other Fluid Compositions

The present and compositions can include a critical, near critical, orsupercritical (densified) fluid and an antimicrobial agent or a gaseouscomposition of an antimicrobial agent. The densified fluid can be a nearcritical, critical, supercritical fluid, or another type of fluid withproperties of a supercritical fluid. Fluids suitable for densificationinclude carbon dioxide, nitrous oxide, ammonia, xenon, krypton, methane,ethane, ethylene, propane, certain fluoroalkanes (e.g.,chlorotrifluoromethane and monofluoromethane), and the like, or mixturesthereof. Suitable fluids include carbon dioxide.

In an embodiment, the present compositions or methods include densifiedcarbon dioxide, medium chain peroxycarboxylic acid, and medium chaincarboxylic acid. Such a composition can be referred to as a densifiedfluid medium chain peroxycarboxylic acid composition. In anotherembodiment, the antimicrobial composition includes the fluid, anantimicrobial agent, and any of the optional or added ingredients, butis in the form of a gas.

Densified fluid antimicrobial compositions can be applied by any ofseveral methods known to those of skill in the art. Such methods includeventing at an object a vessel containing densified fluid andantimicrobial agent. The aqueous phase, which includes hydrogenperoxide, is advantageously retained in the device. The vented gasincludes an effective amount of antimicrobial agent making the densifiedfluid peroxycarboxylic acid compositions effective antimicrobial agents.

Because of the high pressure nature of the densified fluid compositionsof the invention, these compositions are typically applied by venting avessel containing the composition through a pressure relief device thatis designed to promote rapid efficient coverage of an object. Devicesincluding such a pressure relief device include sprayers, foggers,foamers, foam pad applicators, brush applicators or any other devicethat can permit the expansion of the fluid materials from high pressureto ambient pressure while applying the material to an object. Thedensified fluid peroxycarboxylic acid composition can also be applied toan object by any of a variety of methods known for applying gaseousagents to an object.

Densified fluid antimicrobial compositions can be made by reacting anoxidizable substrate with an oxidizing agent in a medium comprising adensified fluid to form an antimicrobial composition. This reaction istypically carried out in a vessel suitable for containing a densifiedfluid. Reacting can include adding to the vessel the oxidizablesubstrate and the oxidizing agent, and adding fluid to the vessel toform the densified fluid. In an embodiment, the reaction is between amedium chain carboxylic acid and hydrogen peroxide to form thecorresponding peroxycarboxylic acid. The hydrogen peroxide is commonlysupplied in the form of an aqueous solution of hydrogen peroxide.

Supercritical, subcritical, near supercritical, and other dense fluidsand solvents that can be employed with such fluids are disclosed in U.S.Pat. No. 5,306,350, issued Apr. 26, 1994 to Hoy et al., which isincorporated by reference herein for such disclosure. Supercritical andother dense forms of carbon dioxide, and cosolvents, co-surfactants, andother additives that can be employed with these forms of carbon dioxideare disclosed in U.S. Pat. No. 5,866,005, issued Feb. 2, 1999 toDeSimone et al., which is incorporated by reference herein for suchdisclosure.

Making Medium Chain Peroxycarboxylic Acid Compositions

The compositions of or used in the methods of the invention can be madeby combining or reacting the medium chain carboxylic acid and theoxidizing agent, such as hydrogen peroxide. Combining or reacting mediumchain carboxylic acid and oxidizing agent results in production ofmedium chain peroxycarboxylic acid. In an embodiment, combining includesmixing. The formulation combined for making the present compositions canalso include the solubilizer, the acidulant, the carrier, stabilizingagent, mixtures thereof, or the like. In an embodiment, the formulationincludes solubilizer. Alternatively, one or more (e.g., at least one) ofthe solubilizer, the acidulant, the carrier, or mixtures thereof, can beadded after production of some or all of the peroxycarboxylic acid.

In an embodiment, the present invention includes a method of making amedium chain peroxycarboxylic acid. The method can include combining orreacting medium chain carboxylic acid, carrier (e.g., water), oxidizingagent (e.g., hydrogen peroxide), solubilizer, acidulant, and stabilizingagent. The method can include mixing the ingredients at concentrationsof about 1 to about 10 wt-% medium chain carboxylic acid, about 0 toabout 98 wt-% carrier, about 2 to about 30 wt-% oxidizing agent, about 1to about 80 wt-% solubilizer, about 1 to about 50 wt-% acidulant, andabout 0.5 to about 50 wt-% stabilizing agent. The method can includemixing the ingredients at concentrations about 1 to about 10 wt-% mediumchain carboxylic acid, about 5 to about 97 wt-% carrier, about 2 toabout 30 wt-% oxidizing agent, about 1 to about 20 wt-% solubilizer(e.g., microemulsion forming surfactant), about 1 to about 50 wt-%acidulant, and about 0.5 to about 50 wt-% stabilizing agent. The presentcompositions also include compositions in which these combinations ofingredients have come to equilibrium forming medium chainperoxycarboxylic acid.

In an embodiment, the present method produces advantageously high levelsof medium chain peroxycarboxylic acid in advantageously short times.Advantageously short times include, for example, about 24 or fewerhours, about 6 or fewer hours, about 3 or fewer hours, or about 0.5 hr.In an embodiment, high levels of medium chain peroxycarboxylic acid canbe achieved nearly instantaneously. High levels of medium chainperoxycarboxylic acid be achieved by converting 20% or more, 25% ormore, 30% or more, 35% or more, or 40% of the medium chain carboxylicacid to medium chain peroxycarboxylic acid. Such conversions can beachieved at room temperature or in a reaction started at roomtemperature and warmed by an exotherm. Lower temperatures can require alonger time to reach the same amount of conversion. The amount of timeis typically measured from the time that the carboxylic acid, oxidizingagent, solubilizer, and acidulant are combined or reacted.

For example, in an embodiment, the present method can convert 20% ormore of the medium chain carboxylic acid to medium chainperoxycarboxylic acid in about 24 or fewer hours. For example, in anembodiment, the present method can convert about 25% or more of themedium chain carboxylic acid to medium chain peroxycarboxylic acid inabout 24 or fewer hours. For example, in an embodiment, the presentmethod can convert about 30% or more of the medium chain carboxylic acidto medium chain peroxycarboxylic acid in about 24 or fewer hours. Forexample, in an embodiment, the present method can convert about 35% ormore of the medium chain carboxylic acid to medium chainperoxycarboxylic acid in about 24 or fewer hours. For example, in anembodiment, the present method can convert about 40% of the medium chaincarboxylic acid to medium chain peroxycarboxylic acid in about 24 orfewer hours.

In an embodiment, making the present compositions includes forming amicroemulsion. A microemulsion can be formed by mixing the desiredingredients including a microemulsion forming surfactant. The method caninclude combining or mixing the ingredients at concentration of about 1to about 10 wt-% medium chain carboxylic acid, about 5 to about 97 wt-%carrier (e.g., water), about 2 to about 30 wt-% oxidizing agent, about 1to about 20 wt-% microemulsion forming surfactant, and about 1 to about50 wt-% stabilizer. The present compositions also include compositionsin which these combinations of ingredients have come to equilibriumforming medium chain peroxycarboxylic acid. The components can be addedin any of a variety of orders. In an embodiment, formation of the mediumchain peroxy carboxylic acid can proceed rapidly after the addition ofthe microemulsion forming surfactant. Although not limiting to thepresent invention, it is believed that the formation of themicroemulsion can significantly increase the effective surface area ofthe medium chain carboxylic acid (as micro-droplets) for reaction.

The present compositions can be made in a plant as a concentrate andshipped to an end user who need only dilute the concentrate to form ause composition. The present medium chain peroxycarboxylic acidcompositions can also be made at the site of use. For example, theproduct can be shipped as a two or more part composition or as a kit.The user can then combine the two or more compositions or components ofthe kit to produce the present medium chain peroxycarboxylic acidcompositions. Alternatively, a system of formulating equipment andcontainers of raw materials can be provided at the site of use, andprogrammed or operated to mix and disperse the present medium chainperoxycarboxylic acid compositions.

In an embodiment, the product can be supplied as a two or more partcomposition. In certain embodiments, one composition can includecarboxylic acid and one or more (e.g., at least one) of solubilizer,acidulant, carrier, stabilizing agent, mixtures thereof, or the like.The second composition can include oxidizing agent and one or more(e.g., at least one) of solubilizer, acidulant, carrier, stabilizingagent, mixtures thereof, or the like. Alternatively, the solubilizer,acidulant, carrier, stabilizing agent mixtures thereof, or the like canbe supplied as additional composition(s). In certain embodiments, onecomposition can include carboxylic acid and at least one of oxidizingagent, solubilizer, acidulant, carrier, stabilizing agent, mixturesthereof, and the like. The second composition can include at least oneof fragrance, odor counteractant, emollient, other incompatibleingredient, oxidizing agent, solubilizer, acidulant, carrier,stabilizing agent, mixtures thereof, and the like.

In an embodiment, the pH of a concentrate composition can be less thanabout 1 or about 2. In an embodiment, the pH of a 1% or 1.5% solution ofthe mixture in water is about 1 or 2 to about 7, depending on the othercomponents of the 1% solution. In an embodiment, the pH of a usecomposition can be from about 2 to about 7 depending on the othercomponents.

Some examples of representative concentrations of ingredients useful inthe present methods of making medium chain peroxycarboxylic acidcompositions can be found in Tables G and H, in which the values aregiven in wt-% of the ingredients in reference to the total compositionweight. In certain embodiments, the proportions and amounts in TablesG-H can be modified by “about”. The present compositions also includecompositions in which these combinations of ingredients have come toequilibrium forming medium chain peroxycarboxylic acid.

TABLE G Ingredient wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% medium chain1-10 3-8 4-6 2-8 3-6 1-10 3-8 3-6 carboxylic acid solubilizer 1-80  2-70 3-65  5-70 10-65 1-25  3-15  4-10 carrier 0-98  5-90 10-80 0.2-60  5-20 5-97 15-70 30-75

TABLE H Ingredient wt-% wt-% wt-% wt-% wt-% wt-% wt-% wt-% medium chain1-10 3-8  4-6 2-8 3-6 1-10 3-8 3-6 carboxylic acid solubilizer 1-80 2-70 3-65  5-70 10-65 1-25  3-15  4-10 carrier 0-98 5-90 10-80 0.2-60   5-205-97 15-70 30-75 oxidizing agent 2-30 2-25  4-20  2-25  4-20 2-30  4-20 6-10 acidulant 1-50 2-40  3-40  2-40  3-40 1-50  3-35  5-30 stabilizingagent 1-50 1-10 1-5  1-10 1-5 1-50 1-5 1-3Additional Methods of Reducing Arthropod Population

The present invention relates to methods for reducing the population of(e.g., killing) arthropods employing compositions including medium chaincarboxylic acid, and to the compositions. The methods include applying amedium chain carboxylic acid (e.g., octanoic acid) composition to anarthropod or a surface or area suspected of housing an arthropod. Themethod can include contacting the arthropod with the medium chaincarboxylic acid composition in an amount and time sufficient to kill thearthropod. The medium chain carboxylic acid composition can include the“base material” for one or more of the exemplified compositions. Themedium chain carboxylic acid composition can include the present mediumchain peroxycarboxylic acid composition aged to the point that itincludes small or insignificant amounts of peroxycarboxylic acid orhydrogen peroxide.

The present invention may be better understood with reference to thefollowing examples. These examples are intended to be representative ofspecific embodiments of the invention, and are not intended as limitingthe scope of the invention.

EXAMPLES Example 1 Medium Chain Peroxycarboxylic Acid CompositionExhibited Cockroach Ovicide Activity

A medium chain peroxycarboxylic acid composition according to thepresent invention was evaluated for ovicidal activity against Germancockroach eggs and compared to conventional and control compositions.

Experiment 1

Materials and Methods

Four compositions were evaluated as potential cockroach ovicides. Thesecompositions included a medium chain peroxycarboxylic acid composition(e.g., Formulas AB and AC, Table 27, Example 8 (with and withoutfragrance, respectively)), a quaternary ammonium sanitizer composition(SWAT), a first insect growth regulator composition (Nyguard), and asecond insect growth regulator composition (Gentrol). Four rates(concentrations/amounts) of each were tested along with a water control.The concentrations employed are shown in the following table (Table 1).For each treatment, 20 mature gravid females were soaked in testsolutions for 30 minutes. The cockroaches were then removed from theliquid and placed into escape-proof containers to allow the nymphs tohatch out along with standard food, water, and harborage. After a week,the containers were checked for emergence of nymphs. Containers werechecked again one month after treatment, though there was no difference.

TABLE 1 Concentrations (wt-%) Tested in this Experiment Product Rate 1Rate 2 Rate 3 Rate 4 Rate 5 Gentrol 0 0.39 0.78 1.6 3.9 Nyguard 0 0.150.30 0.60 1.5 SWAT 0 0.39 0.78 1.6 3.9 medium chain 0 0.50 1 2 5peroxycarboxylic acid medium chain 0 0.50 1 2 5 peroxycarboxylic acidResults

The results obtained for ovicidal activity against cockroach eggs aresummarized in Table 2.

TABLE 2 Nymphal Emergence by Treatment Product Rate 1 Rate 2 Rate 3 Rate4 Rate 5 Gentrol Yes Yes Yes Yes No Nyguard Yes Yes Yes Yes No SWAT YesYes Yes Yes No medium chain Yes No No No No peroxycarboxylic acid mediumchain Yes No No No No peroxycarboxylic acid

Application of each of the four of the products resulted in no nymphalemergence at the highest concentrations applied. Application of anembodiment of the present medium chain peroxycarboxylic acid compositionresulted in no nymphal emergence at concentrations as low as 0.5%(lowest concentration tested). This indicates that the present mediumchain peroxycarboxylic acid compositions possess practical ovicidalproperties for use against German cockroaches.

Experiment 2

Materials and Methods

Medium chain peroxycarboxylic acid (Formula AB) was prepared as a 2%aqueous solution in a 100 ml batch. Tubs were prepared for housingcockroaches. That is, each tub was given a small dish of crushed rodentchow, a small water bottle with wick, and a harborage. Seven week oldfemale German cockroaches were counted into groups of ten. Each group often was then immersed in liquid depending on treatment (Table 3). Afterimmersion, cockroaches were placed onto paper towels prior to gettingplaced into their respective tubs. For the control treatment, tencockroaches were soaked in water for 30 seconds.

Results

After three weeks, the numbers of nymphs were counted in each tub. Alladult cockroaches immersed in sanitizer were killed regardless oftreatment; all cockroaches soaked in water survived. The results areshown in Table 3.

TABLE 3 Treatments Employed and Results Obtained in Experiment 2 SoakNumber of Treatment Time(s) Nymphs medium chain peroxycarboxylic acid 50 medium chain peroxycarboxylic acid 30 0 Water 30 23

Medium chain peroxycarboxylic acid (Formula AB) has ovicidal propertiestowards German cockroach eggs in conditions similar to field settings.Follow up experiments could investigate lower concentrations and evenfaster contact times.

Example 2 Medium Chain Peroxycarboxylic Acid Composition ExhibitedInsecticide Activity Against a Variety of Insects

A medium chain peroxycarboxylic acid composition according to thepresent invention was evaluated for insecticide activity against severaltypes of insects and compared to conventional and control compositions.

Materials and Methods

An automated sprayer was calibrated to apply 1 gram of liquid to theinside of a 16-oz glass jars as it swept across. For each test, one jarof each test species was placed on the shelf in the spray tower. Thesejars were then all dosed with a single sweep of the spray tower. Thetreatment was replicated once with a second set of jars containinginsects. The sprayer was rinsed with water between treatments. A set ofwater control treatments was run after the treatment-group tests werecomplete to measure contamination if present. Mortality was thenrecorded at 60 min, 120 min, and 24 hours after treatment.

For the first test, 7 insect species (red flour beetle, late-instarIndian meal moth larvae, cow pea weevil, Surinam cockroach, sawtoothedgrain beetle, German cockroach, and American cockroach) were treatedwith 4 different concentrations of medium chain peroxycarboxylic acid(Formula AB at 0.13%, 0.78%, 2% and 5%) and water control. There weretwo replicates of each treatment group and one replicate of controls.After 24 hours, the number dead were recorded for each jar. There were10 insects per jar for all species except American cockroach which had 5per jar. The data obtained are shown below (Table 4).

The second experiment compared Dawn Ultra (brand dishwashing detergent)and medium chain peroxycarboxylic acid (Formula AB) on several cockroachspecies (German, American, Brown-Banded, Surinam, Oriental) at twodifferent concentrations (4% and 8%) dosed in the same manner asdescribed above. For non-German cockroaches, each jar contained 10cockroaches that were a mixture of males, females, adults and oldernymphs. Each jar of German cockroaches (5 male, 5 gravid female) wasgiven food and water 24 hours after treatment and kept for one week tosee if any nymphal emergence. The results obtained are shown below inTable 5.

For the final experiment, several other sanitizers were compared to themedium chain peroxycarboxylic acid (Formula AB) for efficacy against 7insect species using the spray tower method. Each treatment was preparedas a 10% aqueous solution. Jars of female cockroaches were given foodand water and observed for one week after the test for nymphalemergence. The results obtained are shown below in Table 6.

Results

The results are shown in Tables 4-6.

Some insects (e.g. insects that can infest stored products) were killedwith even the lowest rates of the medium chain peroxycarboxylic acid ofFormula AB applied as a mist (Table 4). It appears that, in general,larger insects require higher concentrations to be killed.

TABLE 4 Medium Chain Peroxycarboxylic Acid (Formula AB) Killed a Varietyof Insects # dead after 24 hours 0.0% Insect water 0.13% 0.78% 2.0% 5.0%Red Flour 10 10 10 10 10 10 10 10 10 Beetle Indian Meal 1 4 4 9 10 8 910 10 Moth Larvae Cow Pea 8 10 10 10 10 10 10 10 10 Weevil Surinam 0 0 00 0 0 0 0 0 Cockroach Sawtoothed 3 10 10 10 10 10 10 10 10 grain beetleGerman 0 0 0 2 3 4 8 10 10 Cockroach American 0 0 0 0 0 0 0 2 3Cockroach

TABLE 5 Medium Chain Peroxycarboxylic Acid (Formula AB) Killed a Varietyof Cockroaches # dead after 24 hours Formula Dawn AB Dawn Formula InsectWater (4%) (4%) (8%) AB(8%) Oriental cockroach 0 3 3 5 3 7 5 8 7American Cockroach 0 4 5 3 4 7 8 6 5 Brown-Banded 0 10 10 10 10 10 10 1010 Cockroach Surinam Cockroach 0 10 10 2 3 10 10 4 7 German cockroach 08 7 10 9 10 10 10 10 German cockroach Yes No No No No No No No No(nymphal emergence)

TABLE 6 Medium Chain Peroxycarboxylic Acid (Formula AB) Killed a Varietyof Cockroaches as Well as or Better Than Other Peracid Compositions andAntimicrobial Agents. Number Killed (out of 10) Material MaterialMaterial Material Formula Insect 1¹ 2² 3³ 4⁴ AB Water German  4  7  0 210 0 Cockroach (male) German  1*  1*  0* 0 9  0* Cockroach (female)Oriental  0  0  0 0 7 0 Cockroach American  0  0  0 0 5 0 Cockroach RedFlour  9 10 10 0 10 6 Beetle Saw-Toothed 10 10 9 10 10 0 Grain BeetleIndian Meal 10 10 10 10 10 0 Moth Cow Pea 10 10 10 10 10 3 Weevil*nymphal emergence after one week ¹Matrixx - first commerciallyavailable mixed C2 and C8 peroxycarboxylic acid composition ²Inspexx -second commercially available mixed C2 and C8 peroxycarboxylic acidcomposition ³commercially available peroxyacetic acid composition⁴SWAT - commercially available quaternary ammonium composition

Example 3 Medium Chain Peroxycarboxylic Acid Composition ExhibitedInsecticide Activity Against Adult Cockroaches

A medium chain peroxycarboxylic acid composition according to thepresent invention was evaluated for insecticide activity against adultcockroaches and compared to conventional and control compositions.

Experiment 1

Materials and Methods

To determine an adequate dose, three concentrations of the medium chainperoxycarboxylic acid of Formula AB were prepared in the lab as 0.5wt-%, 1 wt-% and 2 wt-% aqueous solutions in 500 ml batches. Four 16-oz.jars, each containing ten adult male German cockroaches were preparedfor each treatment. This test included placing 5 inch circles of filterpaper into plastic bags with 100 ml of each solution. Each bag wasfilled with air and shaken vigorously to give a light foam on each pieceof filter paper. Cockroaches were then exposed to the foam coveredfilter paper using standard forced exposure methodology. Briefly, thisforced exposure method included inverting and forcing the jar onto thetreated planar surface to cause the insects to rest on the filter paper.The inner lip near the open side of the jars were greased to prevent theinsects from climbing up into the jar. Filter paper was remoistenedevery hour for the first 8 hours using 5 ml of water per piece.Mortality was observed as described above.

Results

Several jars of male cockroaches were treated with a 2 wt-% foam of themedium chain peroxycarboxylic acid of Formula AB applied with a Foam-Itpump up roamer. One-hundred percent kill was achieved in all replicatesafter one minute of exposure. After exposure insects were transferred torecovery containers with food and water, but no recovery was observed.The rapid rate of death indicates that something in addition tosuffocation (drowning) killed the cockroaches.

Experiment 2

Materials and Methods

A follow up study compared 4 different products applied as foams. Theseproducts included the medium chain peroxycarboxylic acid of Formula AB(2%), the Base Material (2%), LAS Acid (0.16%, which corresponds to theamount in the medium chain peroxycarboxylic acid of Formula AB), andsodium laurel sulfate (0.16%). Each product was made up in a 300 grambatch and was applied as dry foam to four jars that each contained tenadult male cockroaches using Foam-It pump up foamers.

Results

Employing foam treatment with the medium chain peroxycarboxylic acid ofFormula AB, within ten minutes all cockroaches in all treated jars weredead. This indicates that foam the foam form of the medium chainperoxycarboxylic acid of Formula AB is a more powerful insecticide, atleast against cockroaches, than the liquid form of this composition (seeExperiment 3 below).

Experiment 3

Materials and Methods

Six compositions were evaluated, each at three different rates, to helpdetermine what components of the medium chain peroxycarboxylic acid ofFormula AB are most insecticidal. Each formula was normalized to themedium chain peroxycarboxylic acid of Formula AB at a concentration of2% with respect to total percent fatty acid (Mandate & Mandate Plus(commercially available fatty acid sanitizer compositions) or totalpercent peracid (first commercially available mixed C2 and C8peroxycarboxylic acid composition (Maxtrixx) and commercially availableperoxyacetic acid composition (Oxonia)). Also included was Base Materialwhich included the components of Formula AB but hydrogen peroxide wasreplaced with water and peroxyoctanoic acid was replaced with octanoicacid. All formulas are listed in Table 7. Control consisted of tapwater.

Each formula was made up in 100 g batches and used to moisten 15 cmdiameter round pieces of filter paper. There were 4 replicates of eachtreatment and 8 replicates of controls. Each piece of treated filterpaper was then placed on the lab bench. Each jar containing 10 adultmale German cockroaches was then inverted and hit on its respectivepiece of paper causing the cockroaches to fall and remain on the dampfilter paper. Cockroaches were exposed for four hours; every hour, 5 mlof water were added to each piece of paper to keep it moist. Mortalitywas observed constantly for the first hour and then was checked everyhalf hour until 4 hours. After the 4 hour exposure, each jar ofcockroaches was given standard food and water. Cockroaches were checkedagain after setting in the lab over the weekend to see if there was anyrecovery.

TABLE 7 Compositions Applied as Liquid Fatty Acid Peracid CompositionWt-% Amt. (ppm) (ppm) Mandate 0.56 Low 375 0 Mandate 1.12 Med. 750 0Mandate 2.24 High 1500 0 Mandate Plus 0.54 Low 375 0 Mandate Plus 1.07Med. 750 0 Mandate Plus 2.14 High 1500 0 mixed C2 and C8 0.21 Low 0 100peroxycarboxylic acid composition 0.41 Med. 0 200 0.82 High 0 400peracetic acid 0.20 Low 0 100 composition 0.40 Med. 0 200 0.80 High 0400 medium chain 1.00 Low 375 100 peroxycarboxylic acid 2.00 Med. 750200 4.00 High 1500 400 Base Material 1.00 Low 375 0 2.00 Med. 750 0 4.00High 1500 0Results

Table 8 reports results obtained contacting cockroaches with liquidforms of several different compositions. Employing the medium chainperoxycarboxylic acid of Formula AB, treatment at the high rate (2%) had100% moribundity after 4 hours, but many recovered. No mortality wasobserved in any of the 8 control treatments. The medium chainperoxycarboxylic acid composition killed cockroaches as well as orbetter than each of the commercially available products tested.

TABLE 8 Cockroach Kill by Liquid Compositions % Killed After 72 hoursand Amount Composition Low Medium High Mandate Average 0 0 8 Std Error 00 5 Mandate Plus Average 0 0 30 Std Error 0 0 14 mixed C2 and C8 Average0 0 8 peroxycarboxylic acid composition Std Error 0 0 5 peracetic acidAverage 40 8 25 composition Std Error 19 5 15 medium chain Average 3 1063 peroxycarboxylic acid Std Error 3 4 19 base material Average 0 8 20Std Error 0 8 7Experiment 4Materials and Methods

The methods of Experiment 3 were employed with the compositions listedin Table 9.

Results

The results are shown in Table 9. The medium chain peroxycarboxylic acidcomposition killed cockroaches better than the commercially availableproduct tested.

TABLE 9 Cockroach Kill by Liquid Compositions Average % Kill CompositionWt-% (24 hrs) Std Error peracetic acid 0.2 3 2 composition 0.4 0 0 0.8 22 medium chain 1 0 0 peroxycarboxylic acid 2 38 16 4 80 14 Base Material1 0 0 2 12 7 4 33 13 Water 0 0 0Experiment 5Materials and Methods

The methods of Experiment 3 were employed with the compositions listedin Table 10. Briefly: Each treatment contained 10 male Germancockroaches (7 weeks old). Each composition was made up as 100 grambatches at 1% concentration. The pH's were adjusted using beads ofsodium hydroxide and pH paper. The 50:50 blend was made by adding 0.5grams of each concentrate to a flask and then adding 99 grams of water.Mortality was checked after exposure of the cockroaches for 24 hours.

Results

The results are shown in Table 10. The C8 medium chain peroxycarboxylicacid composition of Formula AB appeared to show reduced efficacy abovepH 3. There was no 15 significant difference in efficacy between C8, C8plus C9, and C9 compositions.

TABLE 10 Cockroach Kill by Liquid Compositions Average % Kill StdComposition Wt-% (24 hrs) Error pH 1 1 23 6 C8 medium chainperoxycarboxylic acid composition (Formula AB) pH 3 1 23 6 C8 mediumchain peroxycarboxylic acid composition pH 5 1 0 0 C8 medium chainperoxycarboxylic acid composition pH 7 1 3 3 C8 medium chainperoxycarboxylic acid composition pH 1 1 23 11 C8 plus C9 medium chainperoxycarboxylic acid composition pH 1 1 35 15 C9 medium chainperoxycarboxylic acid compositionExperiment 6Materials and Methods

The test compositions were applied with a spray tower as described inExample 2. The compositions employed were the medium chainperoxycarboxylic acid composition of Formula AB and a β-cyfluthrin soldunder the tradename Tempo SC Ultra (Tempo)

Results

The results are shown in Table 11. The medium chain peroxycarboxylicacid composition of Formula AB killed slightly fewer cockroaches thanthe β-cyfluthrin. The rate of kill was similar for both compositions.

TABLE 11 Cockroach Kill by The Present Composition and a TraditionalResidual Insecticide Number Knocked Down or Killed male female malefemale male female male female 1440 1440 2880 2880 Compound wt-% 60 min60 min 120 min 120 min min min min min Tempo 0.2 10 10 10 10 10 10 10 10Tempo 0.2 10 10 10 10 10 10 10 10 Tempo 0.1 10 10 10 10 10 10 10 10Tempo 0.1 10 10 10 10 10 10 10 10 Tempo 0.05 10 10 10 10 10 10 10 10Tempo 0.05 10 10 10 10 10 10 10 10 Tempo 0.03 10 10 10 10 10 10 10 10Tempo 0.03 10 10 10 10 10 10 10 10 Water 1 0 1 0 1 0 0 1 0 0 Water 1 0 00 0 0 0 0 0 0 Formula AB 4 10 8 10 8 10 8 10 9 Formula AB 4 10 9 10 9 1010 10 10 Formula AB 2 9 8 9 7 10 7 10 7 Formula AB 2 10 8 10 8 10 7 10 7Formula AB 1 8 5 8 4 8 5 8 4 Formula AB 1 10 5 10 4 10 5 10 4 Formula AB0.5 2 0 4 0 2 0 4 0 Formula AB 0.5 1 1 0 1 1 0 1 0 Water 2 0 0 0 0 0 0 00 0 Water 2 0 1 0 0 0 0 0 0 0Experiment 7

This experiment evaluated the dose of a present medium chainperoxycarboxylic acid composition according to the present inventionthat killed an individual cockroach.

Materials and Methods

Seven week old male German cockroaches were gassed with carbon dioxideand placed on a 1′×2′ Catchmaster glue board so that their wings weretouching glue with the legs and head free to move. The cockroaches wereimmobilized on the glue board in columns of 20 cockroaches and eachcolumn was a treatment group. Each dosed cockroach received a 10 μL doseof test composition from a micro liter pipette. Each dose was applied sothat most of the dose stayed on the intended body region. The intendedbody regions included head, thorax, and abdomen. After 24 hours,mortality was recorded.

Control compositions included: Formula AB with octanoic acid omitted andreplaced with water; Formula AB with hydrogen peroxide omitted andreplaced with water; and the phosphoric acid and peroxide components ofFormula AB at their same concentration. Formula AB was also testedincluding a fragrance (e.g., Formula AC). Concentrations of testcomposition were selected to achieve close to 100% kill at the highestdose.

Results

The treatments are shown with the results below in Table 12. The lethalconcentration of Formula AC was between 4 and 5% with a 10 μL dose.

TABLE 12 Treating Individual Cockroaches With The Present and ControlCompositions Test Composition Wt-% Region % Mortality Formula AB, NoOctanoic 1 Head 0 Formula AB, No Octanoic 1 Thorax 0 Formula AB, NoOctanoic 1 Abdomen 5 Formula AB, No Octanoic 2 Head 0 Formula AB, NoOctanoic 2 Thorax 0 Formula AB, No Octanoic 2 Abdomen 5 Formula AB, NoOctanoic 5 Head 10 Formula AB, No Octanoic 5 Thorax 5 Formula AB, NoOctanoic 5 Abdomen 10 Formula AB, No Octanoic 10 Head 45 Formula AB, NoOctanoic 10 Thorax 50 Formula AB, No Octanoic 10 Abdomen 50 Formula AB,No Peroxide 1 Head 0 Formula AB, No Peroxide 1 Thorax 30 Formula AB, NoPeroxide 1 Abdomen 10 Formula AB, No Peroxide 2 Head 10 Formula AB, NoPeroxide 2 Thorax 30 Formula AB, No Peroxide 2 Abdomen 5 Formula AB, NoPeroxide 5 Head 25 Formula AB, No Peroxide 5 Thorax 45 Formula AB, NoPeroxide 5 Abdomen 95 Formula AB, No Peroxide 10 Head 80 Formula AB, NoPeroxide 10 Thorax 85 Formula AB, No Peroxide 10 Abdomen 90 Formula AC 1Head 5 Formula AC 1 Thorax 5 Formula AC 1 Abdomen 5 Formula AC 2 Head 15Formula AC 2 Thorax 20 Formula AC 2 Abdomen 10 Formula AC 5 Head 75Formula AC 5 Thorax 85 Formula AC 5 Abdomen 5 Formula AC 10 Head 100Formula AC 10 Thorax 95 Formula AC 10 Abdomen 100 Control 0 Head 0Control 0 Thorax 0 Control 0 Abdomen 0 Formula AB 2 Head 0 Formula AB 2Thorax 10 Formula AB 2 Abdomen 0 Formula AB 5 Head 25 Formula AB 5Thorax 50 Formula AB 5 Abdomen 40 Formula AC 2 Head 0 Formula AC 2Thorax 5 Formula AC 2 Abdomen 30 Formula AC 5 Head 45 Formula AC 5Thorax 45 Formula AC 5 Abdomen 40 Control 0 Head 5 Control 0 Thorax 0Control 0 Abdomen 5 Formula AC 5 entire 65 Formula AC 10 entire 100Phosphoric Acid + H₂O₂ 5 head 80 Phosphoric Acid + H₂O₂ 5 thorax 50Phosphoric Acid + H₂O₂ 5 abdomen 60 Formula AC 5 dorsal 20 Formula AC 5side 45 Formula AC 10 dorsal 90 Formula AC 10 side 95 Water 0 entire 5Formula AC 3.87 Head 55 Formula AC 3.87 Head 35 Formula AC 3.87 Head 25Formula AC 3.71 Thorax 25 Formula AC 3.71 Thorax 40 Formula AC 3.71Thorax 50 Formula AC 4.83 Abdomen 80 Formula AC 4.83 Abdomen 60 FormulaAC 4.83 Abdomen 60 Water 0 Thorax 5Experiment 8

This experiment evaluated the dose of a present medium chainperoxycarboxylic acid composition according to the present inventionthat killed an individual cockroach while varying volume andconcentration of the test composition.

Materials and Methods

This test was conducted using methods described in Experiment 7. Twentymale cockroaches were used per treatment.

Results

The results are summarized in Table 13. Dilute solutions are just aseffective as more concentrated solutions, so long as the same amount ofthe test composition of Formula AB was delivered.

TABLE 13 Treating Individual Cockroaches With Various Volumes andConcentrations of Formula AC Volume (μL) Wt-% % Mortality 5 10 75 5 1080 5 10 90 10 5 70 10 5 80 10 5 90 15 3.33 80 15 3.33 85 15 3.33 85 202.5 85 20 2.5 75 20 2.5 85 25 2 85 25 2 80 25 2 75 25 0 15 25 0 20 25 020

Example 4 Medium Chain Peroxycarboxylic Acid Composition Exhibited FruitFly Ovicide Activity

A medium chain peroxycarboxylic acid composition according to thepresent invention was evaluated for ovicidal activity against fruit flyeggs and compared to conventional and control compositions.

Materials and Methods

Three compositions were evaluated on fruit fly eggs (Drosophilavirilis). These compositions included the quaternary ammonium productwith the tradename SWAT, the quaternary ammonium composition sold underthe tradename Assur-Ring Red, and Formula AB. This study included 4concentrations of each composition along with water controls. SWAT andFormula AB were added to solution as is, but Assur-Ring Red wasdissolved in hot water first as a stock solution.

Each vial was prepared with standard fly media (Carolina Biologicalinstant potato flake media & yeast) and allowed to set for 24 hours (19grams each). Two mL of solution was then applied to each vial and mixedin. There were 5 replicates per treatment and ten control vials. Tenadult flies were then placed in each vial and were allowed to lay eggsfor five days. The adults were then removed. At 10 days after theinitial seeding date, the number of pupae was recorded in each vial.

TABLE 14 Concentrations (wt-%) tested in this experiment. AB Assur-RingSWAT control 0 0 0 1 0.5 0.39 1.0 2 1.0 0.78 2.0 3 2.0 1.6 4.0 4 5.0 3.910Results

The results are summarized in the following table including T-Testsversus control for each treatment (Table 15). SWAT significantly reducedthe number of pupae at rates as low as 1 oz. per gallon. Assur-Ring didnot have any effect even at 1 Ox label rate. Formula AB significantlyreduced the number of pupae at as a 5% solution (0.0053 grams (conc.)per gram of media), which was at active concentrations an order ofmagnitude less than SWAT.

TABLE 15 Number of pupae ten days after treatment Formula AB Assur-RingSWAT Level # Pupae Level # Pupae Level # Pupae 1 11 1 43 1 0 1 52 1 11 10 1 51 1 54 1 37 1 0 1 25 1 2 1 0 1 33 1 43 T-Test 0.428 22.8 0.867 33.20.185 16.4 2 4 2 62.0 2 0 2 0 2 0.0 2 0 2 0 2 94.0 2 1 2 53 2 53.0 2 1 269 2 51.0 2 6 T-Test 0.583 25.2 0.372 52.0 0.005 1.6 3 0 3 0 3 0 3 12 30 3 0 3 29 3 0 3 0 3 40 3 25 3 3 3 66 3 66 3 17 T-Test 0.700 29.4 0.31218.2 0.008 4.0 4 1 4 20 4 1 4 0 4 0 4 0 4 3 4 27 4 0 4 0 4 0 4 0 4 1 433 4 14 T-Test 0.004 1.0 0.114 16.0 0.006 3.0 C 37 C 29 C 80 C 9 C 21 C57 C 71 C 0 C 48 C 0 Control 35.2 Mean

Example 5 Medium Chain Peroxycarboxylic Acid Composition ExhibitedLarvacide

A medium chain peroxycarboxylic acid composition according to thepresent invention was evaluated for larvacidal activity and compared toconventional and control compositions.

Materials and Methods

Small Fly Larvae

Formula AB was evaluated as a foam on fly media seeded by differentspecies of small fly (phorid, large fruit fly, small fruit fly). Foreach treatment, fly media was prepared according to standard protocolrespective to each species and was seeded with approximately 20 adultflies for 48 hours. After seeding, foam was applied to the top 1″ abovethe media in each container using a Foam It pump up foamer. For thewater control, water was applied for the same length of time as the foamto ensure similar amount of solution. After one week, the relativeamount of larval activity was recorded.

House Fly Larvae

The eggs were treated on wet filter paper with a single squirt of sprayand were transferred to another piece of wet filter paper in a Petriplate that had fly media on it with another piece of wet filter paper ontop. For this test, 4% and 8% Formula AB were compared to water control.After 24 hours, each Petri plate was observed under the microscope foractivity.

Results

For small flies, the medium chain peroxycarboxylic acid of Formula ABworked much better than the commercially available dish soap atcontrolling larvae. For house flies, both 4% and 8% solutions of themedium chain peroxycarboxylic acid of Formula AB applied directly toeggs had 100% kill.

TABLE 16 Small Fly Larvacide Activity Relative Number of LarvaeTreatment Large Fruit Fly Small Fruit Fly Phorid Fly Water Many ManyMany 2% Formula AB None Many Few 2% Formula AB Few Many Few 4% FormulaAB None Few Fewer 4% Formula AB Few Few Fewer 8% Formula AB None FewFewer 8% Formula AB None Few Fewer 4% Dawn Ultra Many Many Many Dishsoap4% Dawn Ultra Many Many Many Dishsoap

TABLE 17 House Fly Larvacide Activity Treatment Live Larvae? 4% FormulaAB No 4% Formula AB No 8% Formula AB No 8% Formula AB No water Yes waterYes

Example 6 Compositions Including Medium Chain Peroxycarboxylic Acid andSolubilizer

Tables 18-22 present illustrative examples of the present compositionsincluding medium chain peroxycarboxylic acid and solubilizer. Quantitiesin the tables are in wt-%.

TABLE 18 Examples of Compositions Including Solvent SolubilizerIngredient A B C D E Medium Chain 18 1.6 1.4 1.6 2.9 PeroxycarboxylicAcid Medium Chain 3.4 3.6 3.7 3.6 2.4 Carboxylic Acid Solubilizer 60 4060 60 40 Carrier 25 22 25 22 22 Oxidizing Agent 7.0 6.6 7.0 6.9 6.9Acidulant 2 25 2 5 25 Stabilizing Agent 1.2 1.2 1.2 1.2 1.2

In each of compositions A-Q: the medium chain peroxycarboxylic acid wasperoxyoctanoic acid; the medium chain carboxylic acid was octanoic acid;the carrier was water; the oxidizing agent was hydrogen peroxide(supplied from a 35% solution); and the stabilizing agent was HEDP(supplied as Dequest 2010 which includes 60 wt-% HEDP).

In each of compositions A-L, O, P, and Q: the acidulant was concentratedsulfuric acid. In compositions M and N, the acidulant was phosphoricacid (supplied as 85% and 75% phosphoric acid, respectively).

The solubilizer was varied among these compositions. In compositions Aand B, the solubilizer was polyethyleneglycol 300. In compositions C, D,and E, the solubilizer was monomethyl ether of polyethyleneglycol (MPEG550). In composition F, the solubilizer was nonionic surfactant,specifically Pluronic 17R4 an (PO)_(x)(EO)_(y)(PO)_(x) reverse triblockcopolymer with 40% EO and 60% PO. In composition G, the solubilizer waspolyethyleneglycol 300 plus LAS acid (98% linear dodecylbenzene sulfonicacid). In composition H, the solubilizer was polyethyleneglycol 300 plus1-octane sulfonate (supplied under the tradename NAS-FAL as 38% active).In composition I, the solubilizer was polyethyleneglycol 300 plus DowfaxHydrotrope acid (C₆ alkylated diphenyl oxide disulfonic acid). Incomposition J, the solubilizer was dimethyl ether of polyethyleneglycol(PolyDME250) and LAS acid. In composition K, the solubilizer wasdimethyl ether of polyethyleneglycol (PolyDME250) and NAS-FAL. Incomposition L, the solubilizer was dimethyl ether of polyethyleneglycol(PolyDME250) and Dowfax Hydrotrope acid. In compositions M, N, O and P,the solubilizer was dimethyl ether of polyethyleneglycol (PolyDME250)and NAS-FAL. In composition Q, the solubilizer was dimethyl ether ofpolyethyleneglycol (PolyDME250) and NAS acid (supplied as 93% 1-octanesulfonic acid).

These compositions were made from a composition including 5 wt-% mediumchain carboxylic acid.

In each of compositions R-Z: the medium chain peroxycarboxylic acid wasperoxyoctanoic acid; the medium chain carboxylic acid was octanoic acid;the carrier was water; the oxidizing agent was hydrogen peroxide(supplied from a 35% solution); and the stabilizing agent was HEDP(supplied as Dequest 2010 which includes 60 wt-% HEDP). In compositionsR and S, the acidulant was phosphoric acid (supplied as 75% phosphoricacid). In each of compositions T, U, and V, the acidulant was reagentgrade, 98%, concentrated sulfuric acid (15 wt-%) and phosphoric acid (23wt-%) (supplied as 75% phosphoric acid). In compositions W, X, Y, and Z,the acidulant was concentrated sulfuric acid (25 wt-%) and phosphoricacid (14 wt-%) (supplied as 75% phosphoric acid).

TABLE 19 Examples of Compositions Including Solvent Solubilizer andSurfactant Solubilizer Ingredient F G H I J K L M N O P Q Medium Chain0.8 0.7 1.1 1.1 0.9 2.1 1.6 0.7 0.9 5.0 not 5.0 Peroxycarboxylic Acidmeasured Medium Chain 4.3 4.4 4.0 4.0 4.2 4.2 3.1 4.4 4.2 0.2 <5 0.2Carboxylic Acid Solvent Solubilizer 0 40 40 40 42 44 42 34 29 28 28 28Surfactant Solubilizer 45 5 2 5 8 6 7 6 4 6 6 10 Carrier 37 30 33 30 2921 24 26 28 28 26 24 Oxidizing Agent 7.0 6.9 6.8 6.9 6.1 6.4 6.5 6.7 6.56.9 8.7 6.9 Acidulant 5 7 7 7 8 15 15 21 26 25 25 25 Stabilizing Agent1.2 6 6 6 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2

TABLE 20 Examples of Compositions Including Surfactant SolubilizerIngredient R S T U V W X Y Z Medium Chain 0.5 0.4 1.0 1.0 0.7 3.8 3.73.8 3.5 Peroxycarboxylic Acid Medium Chain 4.6 4.6 3.1 3.1 3.4 2.6 2.72.6 2.9 Carboxylic Acid Surfactant Solubilizer 17 20 20 20 20 20 20 2020 Carrier 32 29 27 27 27 24 24 24 24 Oxidizing Agent 8.0 8.3 9.2 9.29.3 8.6 8.7 8.6 8.7 Acidulant 36 36 38 38 38 39 39 39 39 StabilizingAgent 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4

TABLE 21 Examples of Compositions Including Anionic Surfactant and/orMicroemulsion Solubilizer Ingredient AA AA-O BB CC DD EE FF GG HH II JJKK Medium Chain 1.5 2.0 1.2 1.4 1.3 1.4 1.1 1.0 1.2 1.0 1.1 1.3Peroxycarboxylic Acid Medium Chain 3.6 2.7 2.9 2.5 2.6 2.5 2.8 2.9 2.93.1 3.0 2.6 Carboxylic Acid Solubilizer 8 5 5 9 4 4 6 4 5 5 5 4 Carrier41 45 69 52 59 60 62 56 67 67 67 55 Oxidizing Agent 7.7 7.4 6.3 7.8 8.07.6 7.9 8.0 7.8 7.3 7.8 8.1 Acidulant 36 36 14 25 23 23 18 26 14 15 1427 Stabilizing Agent 2.4 2.4 1.8 2.3 2.3 2.3 2.3 2.3 1.8 1.8 1.8 2.0Ingredient LL MM NN OO PP QQ RR SS TT UU VV Medium Chain 1.4 1.1 1.5 not0.9 0.5 0.54 3.4 0.2 1.0 0.4 Peroxycarboxylic Acid determined MediumChain 2.5 2.7 2.3 <3.8 3.1 3.3 3.3 0.5 3.6 2.8 3.4 Carboxylic AcidSolubilizer 4 4 4 5 1 2 4 10 6 10 22 Carrier 56 57 57 40-50 60 59 58 5354 51 39 Oxidizing Agent 7.8 6.9 6.5 <8 7.1 7.5 7.5 5.6 7.8 8.0 7.7Acidulant 26 26 26 26 26 26 26 26 1.8 1.8 1.8 Stabilizing Agent 2.3 2.32.3 2.3 2.3 2.3 2.3 2.3 27 27 27

The solubilizer was varied among these compositions. In composition R,the solubilizer was 1-octane sulfonate (1.9 wt-%) and Tegotens EC-11 (abutoxy capped alcohol ethoxylate, a fast wetting surfactant) (15 wt-%).In compositions S, T, and W the solubilizer was Tegotens EC-11. Incompositions U and Y, the solubilizer was Dehypon LS-54 (R(EO)₅(PO)₄, afast wetting surfactant). In compositions V and Z, the solubilizer wasDehypon LT-104 (a butyl capped alcohol ethoxylate). In composition X,the solubilizer was LF-221 (a butoxy capped alcohol ethoxylate).

In each of compositions AA-VV: the medium chain peroxycarboxylic acidwas peroxyoctanoic acid; the medium chain carboxylic acid was octanoicacid; the carrier was water; the oxidizing agent was hydrogen peroxide(supplied as 35% hydrogen peroxide in water); and the stabilizing agentwas HEDP (supplied as Dequest 2010, which includes 60 wt-% HEDP).

In each of compositions AA, AA-O, DD, EE, GG, KK, LL, MM, NN, OO, PP,QQ, RR, SS, TT, UU, and VV the acidulant was phosphoric acid (suppliedas 75% phosphoric acid). In composition BB, HH the acidulant wasconcentrated sulfuric acid (reagent grade, 98%). In composition CC, theacidulant was methane sulfonic acid (99.5%+Aldrich). In composition FF,the acidulant was nitric acid (supplied as 70% nitric acid). Incomposition II, the acidulant was concentrated sulfuric acid (technicalgrade, 93%). In composition JJ, the acidulant was sulfuric acid(supplied as 50% sulfuric acid).

The solubilizer was varied among these compositions. In compositions AA,AA-O, BB, CC, DD, FF, LL, HH, II, and JJ, the solubilizer was 1-octanesulfonate. In compositions EE and GG, the solubilizer was 1-octanesulfonate (3.8 wt-%) and Dehypon LS-54 (0.2 wt-%). In composition KK,the solubilizer was 1-octane sulfonate (NAS-FAL). In composition MM, thesolubilizer was 1-octane sulfonate (3.8 wt-%) and Barlox 12(dodecyldimethyl amine oxide, 30% active) (0.25 wt-%). In compositionNN, the solubilizer was 1-octane sulfonate (3.8 wt-%) and Barlox 12 (0.5wt-%). In composition OO, the solubilizer was 1-octane sulfonate (3.8wt-%) and Barlox 12 (1 wt-%). In compositions PP, QQ, RR, and SS, thesolubilizer was LAS-acid. In composition TT, the solubilizer wasdisodium cocoampho dipropionate (supplied under the tradename Miranol®FBS, which includes 39% solids). In composition UU, the solubilizer wasan aminoproprionate betaine (supplied under the tradename Mirataine®JC-HA, which includes 42% solids). In composition VV, the solubilizerC12-13 alcohol 4 mole EO carboxylic acid (supplied under the tradenameNeodox 23-4, which includes 90% active).

The quantities of medium chain peroxycarboxylic acid were determined incompositions PP, QQ, RR, and SS after 7.5 days at 60° C.

TABLE 22 Examples of Compositions Including Anionic Surfactant and/orMicroemulsion Solubilizer plus Strong Organic Acidulant Ingredient WW XXYY ZZ BA Medium Chain 1.5 1.3 0.5 0.5 0.8 Peroxycarboxylic Acid MediumChain 2.5 2.7 3.5 3.5 3.2 Carboxylic Acid Solubilizer 4 4 4 4 4 Carrier58 58 56 57 71 Oxidizing Agent 7.7 7.6 7.7 8.1 8.2 Acidulant 24 24 26 2511 Stabilizing Agent 1.8 1.8 1.8 1.8 1.8

In each of compositions WW, XX, YY, ZZ, and BA: the medium chainperoxycarboxylic acid was peroxyoctanoic acid; the medium chaincarboxylic acid was octanoic acid; the carrier was water; the oxidizingagent was hydrogen peroxide (supplied as 35% hydrogen peroxide inwater); the stabilizing agent was HEDP (supplied as Dequest 2010, whichincludes 60 wt-% HEDP); and the solubilizer was NAS-FAL.

The acidulant was varied among these compositions. In composition WW,the acidulant was hydroxyacetic acid (supplied as 75% hydroxyaceticacid) (19 wt-%) and sulfuric acid (reagent grade, 98%) (5 wt-%). Incomposition XX, the acidulant was hydroxyacetic acid (supplied as 75%hydroxyacetic acid) (19 wt-%) and methane sulfonic acid (99.5%+Aldrich)(5 wt-%). In composition YY, the acidulant was hydroxyacetic acid(supplied as 75% hydroxyacetic acid). In composition ZZ, the acidulantwas purified hydroxyacetic acid. In composition BA, the acidulant washydroxypropionic acid (supplied as 22% 3-hydroxypropionic acid).

In these compositions the hydroxycarboxylic acids contributed virtuallyno solubilization of the medium chain carboxylic acid. The compositionsrequired solubilizer.

Making the Exemplified Compositions

Table 23 shows the rapid generation of peroxyoctanoic acid achieved inmaking composition KK.

TABLE 23 Generation of Peroxyoctanoic Acid with Time at Room Temperatureand at 120° F. (Composition KK) Minutes at [POOA] Minutes at [POOA] RTwt-% 120° F. wt-% 11 0.61 30 1.46 53 1.09 45 1.38 97 1.11 60 1.23 1301.1 90 1.47 235 1.24 120 1.31 293 1.27 330 1.46 366 1.39 395 1.5

When a high level of sulfuric acid was used as the acidulant (Examplesinclude B, E, O, and Q), a strong exotherm was obtained, and the mediumchain peroxy carboxylic acid was generated rapidly, for example,virtually instantaneously. For some of these compositions, the sulfuricacid needed to be added slowly and with cooling to keep the temperaturebelow 170° F. or below 120° F. Such formulas that can generate mediumchain peroxy carboxylic acids, rapidly or almost instantaneously can beemployed for on site generation at the use location.

The concentrations of peroxyoctanoic acid reported in the presentexamples were determined by a well established and standardizedtitration protocol. First, hydrogen peroxide content was determined byan oxidation-reduction titration with ceric sulfate. After the endpointof this titration was reached, an excess of potassium iodide was addedto the solution. The potassium iodide reacts with peroxycarboxylic acidsto liberate iodine. The liberated iodine was titrated with a standardsolution of sodium thiosulfate to yield the concentration ofperoxycarboxylic acid. The remaining level of carboxylic acid can becalculated.

The octanoic acid employed in the present examples was obtained fromsources including Procter & Gamble Chemicals and includes a minimum of95% octanoic acid with minor amounts of hexanoic acid (ca. 2%), decanoicacid (ca. 2%), and dodecanoic acid (<0.5%).

Example 7 Shear Thinning Viscosity of Compositions Including MediumChain Peroxycarboxylic Acid and Solubilizer

Compositions according to the present invention were evaluated anddemonstrated to have advantageous shear thinning viscosity, which ischaracteristic of microemulsions.

Materials and Methods

Several of the present medium chain peroxycarboxylic acid compositionswere evaluated for viscosity as a function of rate of spindle rotationusing an LVT viscometer and an N2 spindle. The temperature of thecompositions was room temperature (about 75° F.).

Results

The results obtained for determinations of viscosity of the presentcompositions are reported below in Tables 24-26. Decreasing viscositywith increasing spindle rotation rate indicates shear thinning, which ischaracteristic of a microemulsion. Each of the compositions testedshowed shear thinning viscosity.

Conclusions

The shear thinning viscosity of the present compositions ischaracteristic of a structured composition, such as a microemulsion.

TABLE 24 Shear Thinning Viscosity of Composition LL Viscosity Viscosityrpm (cp) rpm (cp) 0.6 3875 2 2260 1.5 2600 2.5 1952 3 1700 4 1380 6 13005 1208 12 863 10 736 30 483 20 468 60 308 50 280 100 204

TABLE 25 Shear Thinning Viscosity of Composition HH Viscosity Viscosityrpm (cp) rpm (cp) 0.6 7000 2 3500 1.5 3500 2.5 2848 3 2200 4 1950 6 15005 1648 12 950 10 976 30 515 20 600 60 315 50 324 100 212

TABLE 26 Shear Thinning Viscosity of Composition KK Viscosity rpm (cp)0.5 4080 1 3120 2 2240 2.5 2016 4 1570 5 1344 10 820 20 520 50 320 100218

Example 8 Compositions Including Medium Chain Peroxycarboxylic Acid andSolubilizer

Table 27 presents additional illustrative examples of the presentcompositions including medium chain peroxycarboxylic acid andsolubilizer. Quantities in the tables are in wt-%.

In each of compositions AB-AQ: the medium chain peroxycarboxylic acidwas peroxyoctanoic acid; the medium chain carboxylic acid was octanoicacid; the carrier was water; the oxidizing agent was hydrogen peroxide(supplied from a 35% solution); the stabilizing agent was HEDP (suppliedas Dequest 2010 which includes 60 wt-% HEDP); and the acidulant wasphosphoric acid (supplied as 75% phosphoric acid). Composition ACincluded fragrance (1 wt-%), specifically a mint apple fragrance.

The solubilizer was varied among these compositions. In each ofcompositions AB-AD, AH, AI, AN, the solubilizer was LAS acid. Incompositions AE and AJ, the solubilizer was LAS acid plus C8 amineoxide. In composition AF, the solubilizer was LAS acid plus n-octylamine. In composition AG, the solubilizer was LAS acid plus C8-dimethylamine. In composition AK, the solubilizer was LAS acid plus alkylateddiphenyl oxide disulfonate (acid form). In composition AL, thesolubilizer was alkylated diphenyl oxide disulfonate (acid form). Incomposition AM, the solubilizer was LAS acid plus alkylated diphenyloxide

TABLE 27 Examples of Compositions Including Surfactant Solubilizer(quantities in wt-%) Ingredient AB AC AD AE AF AG AH AI AJ AK AL AM ANMedium Chain 1.0 1.1 3.1 1.2 1.5 0.9 1.2 1.1 nd 0.9 0.9 nd 0.9Peroxycarboxylic Acid Medium Chain 2.8 2.7 2.0 2.6 2.3 2.9 2.6 2.7 <3.82.9 2.9 <3.8 2.6 Carboxylic Acid Solubilizer 7.8 9.7 11 8.2 7.9 7.9 76.5  8-12 5.7 6.3 8.6 7.8 Carrier 52 51 34 52 52 52 53 53 48-52 54 54 5252 Oxidizing Agent 8.0 8.1 11 8.1 8.2 8.1 8.0 8.1 8 8.1 8.1 8 7.9Acidulant 27 27 36 27 27 27 27 27 27 27 27 27 27 Stabilizing Agent 2.02.0 2.7 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Examples of CompositionsIncluding Surfactant Solubilizer Ingredient AO AP AQ AR AS AT AU AV AWAX AY AZ BC Medium Chain 1.0 0.9 0.9 1.0 nd nd 1.0 1.0 nd nd nd 0.7 0.7Peroxycarboxylic Acid Medium Chain 2.8 2.9 2.9 2.8 <4.3 <4.8 2.9 3.0<3.8 <3.8 <3.8 3.1 3.1 Carboxylic Acid Solubilizer 8-9 4.5 4.3 7.8 7.87.8 7.8 7.8 8 8.3 8.6 7.4 7.8 Carrier 52 56 56 52 52 52 52 52 52 52 5253 52 Oxidizing Agent 8.1 8.2 8.2 8.0 8 8 8.2 8.2 8 8 8 8.2 8.2Acidulant 27 27 27 27 27 27 27 27 27 27 27 27 27 Stabilizing Agent 2.02.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Examples of CompositionsIncluding Surfactant Solubilizer Ingredient BD BE BF BG BH BI BJ BKMedium Chain 1.0 1.0 1.0 0.9 0.9 1.0 1.0 1.1 Peroxycarboxylic AcidMedium Chain 2.8 2.8 2.9 2.9 2.9 2.8 2.8 2.7 Carboxylic Acid Solubilizer12 10 9 10 13 15 14 16 Carrier 48 50 51 50 47 45 46 44 Oxidizing Agent7.8 8.2 7.6 8.3 8.3 8.3 8.2 8.1 Acidulant 27 27 27 14 14 14 14 14Stabilizing Agent 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0disulfonate (acid form) and C8 amine oxide. In composition AO, thesolubilizer was sodium laureth sulfate; suitable sodium laureth sulfatestested include those with n=1 and 3. In composition AP, the solubilizerwas alkylated diphenyl oxide disulfonate (salt form). In composition AQ,the solubilizer was alkylated diphenyl oxide disulfonate (salt form)plus NAS-FAL.

In each of compositions AR-AW: the carrier was water; the oxidizingagent was hydrogen peroxide (supplied from a 35% solution); thestabilizing agent was HEDP (supplied as Dequest 2010 which includes 60wt-% HEDP); the acidulant was phosphoric acid (supplied as 75%phosphoric acid), and the solubilizer was LAS acid.

The medium chain peroxycarboxylic acid and medium chain carboxylic acidwere varied among these compositions. In composition AR, the mediumchain peroxycarboxylic acid was peroxynonanoic acid and the medium chaincarboxylic acid was nonanoic acid (straight chain nonanoic acid). Incompositions AS-AW, the medium chain peroxycarboxylic acid wasperoxyoctanoic acid and peroxynonanoic acid and the medium chaincarboxylic acid was octanoic acid and nonanoic acid; nonanoic acid (asisononanoic acid (which is believed to be a 6 carbon main chain withthree pendant methyl groups)) was present at 0.5, 1, 0.1, 0.2, and 0.3wt-% for AS-AW, respectively.

In each of compositions AX-AZ and BC-BF: the medium chainperoxycarboxylic acid was peroxyoctanoic acid; the medium chaincarboxylic acid was octanoic acid; the carrier was water; the oxidizingagent was hydrogen peroxide (supplied from a 35% solution); thestabilizing agent was HEDP (supplied as Dequest 2010 which includes 60wt-% HEDP); and the acidulant was phosphoric acid (supplied as 75%phosphoric acid).

The solubilizer was varied among these compositions. In composition AX,the solubilizer was LAS acid plus sodium lauryl sulfate. In compositionAY, the solubilizer was LAS acid plus sodium lauryl sulfate and C8dimethyl amine. In compositions AZ and BC-BF, the solubilizer wassecondary alkane sulfonate (a mixture of sulfonated paraffins sold underthe tradename Hostapur SAS).

In each of compositions BG-BK: the medium chain peroxycarboxylic acidwas peroxyoctanoic acid; the medium chain carboxylic acid was octanoicacid; the carrier was water; the oxidizing agent was hydrogen peroxide(supplied from a 35% solution); the stabilizing agent was HEDP (suppliedas Dequest 2010 which includes 60 wt-% HEDP); the solubilizer wassecondary alkane sulfonate (a mixture of sulfonated paraffins sold underthe tradename Hostapur SAS) plus NAS-FAL; and the acidulant was sulfuricacid.

The compositions that included LAS, secondary alkane sulfonate,alkylated diphenyl oxide disulfonate, or sodium lauryl sulfate assolubilizer were foaming compositions. Specifically, compositions AB andAC are foaming compositions

Most of the compositions were phase stable. In particular: CompositionsAX and AY were determined to be phase stable at 60° C. The phase stablecompositions including anionic surfactant (e.g., foaming compositions)exhibited blue tyndall appearance and viscoelasticity. They weremicroemulsions. In fact, only the compositions for which the wt-% ofmedium chain peroxycarboxylic acid was not determined (nd) were notphase stable. That is, they separated into more than one phase after apredetermined time at one or more (e.g., at least one) of 40° F., roomtemperature, 100° F., or 140° F. (60° C.).

The concentrations of peroxyoctanoic acid reported in the presentexamples were determined by a well established and standardizedtitration protocol. First, hydrogen peroxide content was determined byan oxidation-reduction titration with potassium permanganate. After theendpoint of this titration was reached, an excess of potassium iodidewas added to the solution. The potassium iodide reacts withperoxycarboxylic acids to liberate iodine. The liberated iodine wastitrated with a standard solution of sodium thiosulfate to yield theconcentration of peroxycarboxylic acid. The remaining level ofcarboxylic acid can be (and was) calculated.

The peroxycarboxylic acid was titrated at a time after formulation thatwas practical in the laboratory. For example, the peroxycarboxylic acidwas titrated for compositions AB, AD, AE, AF, AG, AH, AK, AL, AO, AP,AQ, AU, AV, AZ, BC, and BD after the sample had sat at room temperaturefor 0, 2 (BD), or 3 (AP, AU, and AV) days. For example, theperoxycarboxylic acid was titrated for compositions AC and BG-BK afterthe sample had sat at 100° F. for 4 days (AC) or 7 days (BG-BK). Forexample, the peroxycarboxylic acid was titrated for compositions AI, AN,AR, BE and BF after the sample had sat at 140° F. (60° C.) for 1 day(AI, AR, and BE) or 4 days (AN and BF).

For composition AB, no decomposition of peroxycarboxylic acid wasobserved upon aging the composition for 7 days at 140° F. (60° C.). Forcomposition AC, no decomposition of peroxycarboxylic acid was observedupon aging the composition for 34 days at 100° F. Other compositionswere also observed to include stable peroxycarboxylic acid.

The octanoic acid employed in the present examples was obtained fromsources including Procter & Gamble Chemicals and includes a minimum of95% octanoic acid with minor amounts of hexanoic acid (ca. 2%), decanoicacid (ca. 2%), and dodecanoic acid (<0.5%).

Fragrance

Certain of the compositions were evaluated for phase stability and forsmell after addition of a fragrance. In particular, compositions AB andAG were evaluated. Fragrances evaluated included Green Meadow (Klabin);Vinegar Mask I (J&E Sozio); Vinegar Mask II (J&E Sozio); amyl acetate;iso-bornyl acetate; and methyl salicylate.

Composition AC included fragrance (1 wt-%), specifically a mint applefragrance which is believed to be or include an alkyl salicylate.Composition AC altered to include 10 wt-% LAS remained single phase at40° F., room temperature, and 70° F.

Foaming

The results in Table 28 show that the present medium chainperoxycarboxylic acid composition produced foam with desirablequalities. This study employed a “FOAM IT” brand tank foamer set toproduce slightly wet foam, 2 turns from the mid point. The foam wasdispensed from use composition at 95-98° F. The foam was sprayed on avertical

TABLE 28 Foaming by the Present Medium Chain Peroxycarboxylic AcidCompositions. Amount in Use Foam Dry Initial Appearance of CompositionSolution (oz/gal) Break Time Time (min) Odor Foam Comments AB 0.17slow, >10 moderate Covers well, wet, foam breaks to spotty about 2 minabout 1/16 inch thick foam, dries to no visible residue AG 0.17slow, >10 moderate Covers well, wet, foam breaks to spotty about 2 minabout 1/16 inch thick foam, dries to no visible residue AH 0.17 faster,95% dry at moderate Covers well, wetter foam breaks to spotty <2 min 10min than above foam, dries to no visible residue AK 0.17 fast, 95% dryat moderate Wetter than above no visible residue about 1 min 10 min AY0.17 fast, 95% dry at strong Very wet, lays flat no visible residueabout 10 sec 10 min AB 0.13 fast, about 10 min low Covers, wet spottyfoam <1 min AG 0.13 fast, about 10 min low Covers, wet streaky foam <1min AH 0.13 very fast, about 10 min low Extremely wet very spotty foam<1 min AK 0.13 very fast, about 10 min low Extremely wet very spottyfoam <1 min AY 0.13 fast, 95% dry at strong Very wet, lays flat novisible residue about 10 sec 10 minstainless steel surface (approximately 15 ft by 15 ft) from a distanceof about 10 ft. The results of Table 28 demonstrate that the presentcompositions provided foam with desirable hang time and density. Each ofthe compositions tested at 1 oz/6 gal. provided foam with desirablecharacteristics, such as the breaking foam was visible for about 5 min,the foam drained well from the vertical surface, exhibited good sheetingdown vertical surface, and dried evenly to no visible residue.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a composition containing “a compound” includes a mixture oftwo or more compounds. It should also be noted that the term “or” isgenerally employed in its sense including “and/or” unless the contentclearly dictates otherwise.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains.

The invention has been described with reference to various specific andpreferred embodiments and techniques. However, it should be understoodthat many variations and modifications may be made while remainingwithin the spirit and scope of the invention.

We claim:
 1. A method of killing an arthropod comprising: providing amedium chain peroxycarboxylic acid concentrate composition comprising:about 0.5 to about 5 wt-% peroxyoctanoic acid; about 1 to about 10 wt-%octanoic acid; about 10 to about 80 wt-% water; about 1 to about 20 wt-%anionic surfactant; about 5 to about 10 wt-% oxidizing agent; about 15to about 35 wt-% inorganic acid; and about 1 to about 5 wt-%sequestrant; wherein the composition is substantially free of shortchain percarboxylic acids, and the composition comprising amicroemulsion, the microemulsion comprising droplets of a diameter of100 nanometers or less; preparing a use composition from the mediumchain peroxycarboxylic acid concentrate composition comprising dilutingabout 0.01 to about 4.0 wt % of the concentrate with about 96 to about99.99 wt % of a diluent; and contacting an arthropod with the usecomposition in an amount and time sufficient to kill the arthropod. 2.The method of claim 1, wherein the medium chain peroxycarboxylic acidcomposition comprises: about 2 or more parts by weight of medium chainperoxycarboxylic acid for each 7 parts by weight of medium chaincarboxylic acid.
 3. The method of claim 1, wherein contacting comprisescontacting the arthropod with a foamed composition.
 4. The method ofclaim 1, wherein contacting comprises contacting the arthropod with awet spray.
 5. The method of claim 1, wherein contacting comprisescontacting the arthropod with an aerosol spray.
 6. The method of claim1, wherein the arthropod comprises an insect.
 7. The method of claim 1,wherein the arthropod comprises an arachnid.
 8. The method of claim 1,wherein the arthropod comprises a centipede, millipede, or sow bug. 9.The method of claim 1, wherein the composition comprises a highconcentration of medium chain peroxyoctanoic acid and the arthropod iscontacted with a low volume of the composition per arthropod.
 10. Themethod of claim 1, wherein the composition comprises a low concentrationof medium chain peroxyoctanoic acid and the arthropod is contacted witha high volume of the composition per arthropod.
 11. The method of claim1, wherein the arthropod comprises an arthropod egg.
 12. The method ofclaim 1, wherein the arthropod comprises an arthropod larvae.
 13. Amethod of killing an arthropod egg comprising: providing a medium chainperoxycarboxylic acid composition comprising: about 0.5 to about 5 wt-%peroxyoctanoic acid; about 1 to about 10 wt-% octanoic acid; about 10 toabout 80 wt-% water; about 1 to about 20 wt-% anionic surfactant; about2 to about 30 wt-% oxidizing agent; about 15 to about 35 wt-% inorganicacid; and about 1 to about 5 wt-% sequestrant; wherein the compositionis substantially free of short chain percarboxylic acids and comprises amicroemulsion, the microemulsion comprising droplets of a diameter of100 nanometers or less; preparing a use composition from the mediumchain peroxycarboxylic acid composition; and contacting an arthropod eggwith the use composition in an amount and time sufficient to kill thearthropod egg.
 14. The method of claim 13, wherein contacting comprisescontacting the arthropod egg with a foamed composition.
 15. The methodof claim 13, wherein the arthropod egg comprises a cockroach egg.
 16. Amethod of killing arthropod larva comprising: providing a medium chainperoxycarboxylic acid composition comprising: about 0.5 to about 5 wt-%peroxyoctanoic acid; about 1 to about 10 wt-% octanoic acid; about 10 toabout 80 wt-% water; about 1 to about 20 wt-% anionic surfactant; about5 to about 10 wt-% oxidizing agent; about 15 to about 35 wt-% inorganicacid; and about 1 to about 5 wt-% sequestrant; wherein the compositionis substantially free of short chain percarboxylic acids, and comprisesa microemulsion, the microemulsion comprising droplets of a diameter of100 nanometers or less; preparing a use composition from the mediumchain peroxycarboxylic acid composition; and contacting an arthropodlarva with the use composition in an amount and time sufficient to killthe arthropod larva.
 17. The method of claim 16, wherein contactingcomprises contacting the arthropod larva with a foamed composition.